![]() To delete your selected Signature, click YES If you decide that you no longer want to have any signature, or want to delete one that you no longer use, you can delete a selected Signature.įrom the Select signature to edit scroll list, select the Signature you want to remove In the Edit signature section, make the appropriate changes to the Signature When ready to send your message, click SENDĪs time passes, or if there is a mistake, you may wish to change your Signature.įrom the Select signature to edit scroll list, select the Signature you want to edit On the Message tab, in the Include group, click Signature » select the desired Signature On the Insert tab, select Signature » select the desired Signature ![]() Place your insertion point where you want the new Signature to appear
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Safely than the the narrow expanse of the Adriatic, the Baltic Sea or theĮnglish Channel? Provide ship or sails adapted to the heavenly breezes,Īnd there will be some who will not fear even that void …. Would have believed that a huge ocean could be crossed more peacefully and Johannes Kepler, letter to Galileo Galilei, 1609.Īs soon as somebody demonstrates the art of flying, settlers from our ![]() There will also be people, who do not shrink from the dreary vastness of Ships and sails proper for the heavenly air should be fashioned. Leonardo da Vinci, Codex on the Flight of Birds, circa 1505. Law, which instrument it is within the capacity of man to reproduce with Leonardo Da Vinci, Codex Atlanticus, describing his (never built)Ī bird is an instrument working according to mathematical If it is well made from starched linen, will rise in the air if turned I have discovered that a screw-shaped device such as this, Roger Bacon, Book of Secret Operations and Natural Magic (Epistola de Secretis Operibus Artis et Naturae, et de Nullitate Magiae), circa 1250. ![]() The air after the manner of a flying bird. Turn an engine, by which the wings, being artificially composed, may beat Likewise an instrument mayīe made to fly withall if one sits in the midst of the instrument, and do If they were full of men also chariots that shall move with unspeakableįorce without any living creature to stir them. Only with one man to steer them, and they shall sail far more swiftly than Of navigation without men to row them, as great ships to brooke the sea, The crater Ibn Firnas on the Moon is named in his honor.įirst, by the figurations of art there be made instruments He is reputed to have attempted flight with man-made wings. What man-made machine will ever achieve the completeĪbbas Ibn Firnas, 852. Of a helicopter, in the form of a childs toy. Returning blades so as to set the machine in motion.īook titled Pao Phu Tau, Fourth Century BC, earliest description Inner part of the jujube tree, using ox-leather straps fastened to Master said, some have made flying cars with wood from the Mounting to dangerous heights and traveling into the vast inane. Someone asked the master about the principles of HRH The Prince Philip, Duke of Edinburgh, forward to The Future of Aeronautics, edited by John E Allen and Joan Bruce, Royal Aeronautical Society, 1970. ![]() ![]() Furthmore the developments themselves change the environment and what may seem desirable or attainable in terms of today can easily be irrelevant in terms of tomorrow. The rate of progress and development is so fast that events have a nasty habit of overtaking predictions. Predicting the future of aeronautics is particularly tempting because there seems so much to predict. Neil Armstrong, speech to joint session of Congress, Year and yet far too little for the next ten. Wilbur Wright, speech accepting the Gold Medal from the Aero Club of France in Paris, 5 November 1908. It is not really necessary to look too far into the future we seeĮnough already to be certain that it will be magnificent. Wilbur Wright, speech accepting the Gold Medal from the Aero Club of Man would not fly for fifty years … Ever since, I have distrusted I confess that in 1901, I said to my brother Orville that ![]() XD And here’s the buttload of info I feel you need for this world. Hope you guys like Foxboro! :D This is actually like the 3rd Foxboro, I just didn’t like the other ones. Since that time, however, Foxboro has transformed from it’s farming roots to a quaint, peaceful community loved by all who visit (and stay.)” Fox, Foxboro was intended to be a small, farming outpost of the ruling power of the day. If you take any photos or build on it etc, i’d love for you to show me, so tag it emperorsims or aelview. But you can still get there, there is a path hehe.Īny issues, please message me. It can also be used as just a secluded lot for your sims, or whatever you would like to “hide” :P It has not been filled in but it does have trees around so it’s also hidden. There is a lot in the far top right of the map, as I was given an idea for an enchanted forest.There are plenty of spawners for all you people who like to gather and collect.I made this with patch 1.57, because if you have a mac like me, you haven’t patched because graphics are aheuiwjs :) It will work with later patches.It is completely base game compatible, you do not need any eps.This is a small world, for us who enjoy small worlds because theyre lag free and or cant load large worlds :P. ![]() If you encounter any issue please message me. I will release a save file eventually, and any special lots/houses I make :) Of course you are allowed to create & upload your own save file if it so pleases you :)īe aware: This is new, if there are bugs I have not yet found them, but I doubt there will be. I envision a tight and friendly community living here. My idea was for a suburban community where sims had backyards that pretty much backed into each other that kids could travel backyard to backyard, playing till the streetlights came on. Who doesn’t need a small world with lots of lots? It shows lot sizes & community/residential lots. Check latest posts tagged #oakwood-plains to find out more.Īelview is perfect for those who want a suburban little tight-knit town for their sims to live in. ♥ĪTTENTION! New Oakwood Plains - version 3.0 - will be released soon. If you’re going to share some gameplay photos taken in this world, please tag them Oakwood Plains. I’m using a lightning mod by Let Them Eat Burnt Waffles (with Lucky Palms water). I believe I will be sharing lots that I’m about to create. Save file with families (made by me, some pics in previous posts) is coming here to download tomorrow! can be found here. New residential and community lots (empty).No university lots (left some community ones).Views are stunning and possibilities are endless! It’s a modified version of University world and it works as a home world. If you’re looking for an awesome new world for your Sims to live in, I have a great news for you - you just found it! ) Download the installer for Vidmore Screen Recorder –> screen-recorder. Go to the giveaway page –> Giveaway LinkĮnter your name and email address to get a free license code Price: $29.90/month How to get the Vidmore Screen Recorder license key for free?įollow these steps to get a free license key for Vidmore Screen Recorder Supported OS: Windows XP/ Vista/ 7/ 8/ 8.1/ 10/ 11 ![]() After installation, run it on your computer. Free download and install Vidmore Screen Recorder for Windows or Mac. Record 2D/3D games, flash games, and online games on PC Now let’s take a look at the program in use.Easily capture your desktop screen activity in any area.Capture online videos from YouTube, Dailymotion, Facebook, TED, and more.Vidmore Free Online Screen Recorder r den bsta gratis programvaran fr skrminspelning online fr PC och Mac. F fler tips och tricks fr inspelningsskrm. Take a screenshot of the whole screen or a single window Vidmore Free Screen Recorder Online lter dig spela in video med webbkamera.Record any audio on your computer, and your voice from the microphone.Record and save high-quality video content from your webcam. ![]() Overall, it is an excellent recorder for everyone. This software is the go-to solution for the different users to do their work. Choose the recording mode, region, and audio settings. Easily add subtitles, annotations, highlights, and overlays to level up your video content. Vidmore Free Video Converter accepts pretty much any. FlexClip is an all-in-one screen recorder and video editor, with which you can edit recordings at will. Indeed, Vidmore Screen Recorder is the most smooth and easy-to-use screen recorder in the market. Vidmore Video Converter is an all-in-one solution for converting videos of all sizes, quality presets, and durations into the desired format, with added options for transforming your video library into whole new categories of multimedia such as Video and Photo collages, and more. You can use this desktop recording tool to make desktop screencasts of online YouTube videos, games, podcasts, webinars, lectures, presentations, Skype calls, online conferences, webcam videos, etc. Our Verdict As we all know, Vidmore Screen Recorder possesses practical tools in recording and other stuff. ![]() With it, you can record any area of the computer screen. Vidmore Screen Recorder is an easy-to-use and professional software for capturing screen and audio simultaneously or separately. ![]() The purpose of conflict in stories is to challenge your characters and push them to their limits. Conflict is also a key part of a story’s plot (see section above). ConflictĪ story is not a story without conflict. The story mountain template is a great way to plan out a story’s plot. And the ending is where all conflicts are resolved, and the story comes to a close. The middle is where the major conflict occurs. The beginning introduces the characters and sometimes shows a minor conflict. In its simplest form, a plot has a beginning, middle and end. It can contain multiple scenes and events. The plot explains what a story is about from beginning to end. The choice of words sets the mood and adds an extra layer of excitement to a story. While a fairy tale such as Cinderella uses light and warm language like magical, glittering, beautiful or happily ever after. For example in horror stories, you may notice dark language being used throughout, such as gore, dismal, damp or vile. Do you want them to be scared, excited or happy? It’s the way you explain and describe a particular location, object or person. The mood is the feeling you want readers to feel when reading your story. The final part of the setting is the mood. For example, you don’t want to be talking about characters using mobile phones in the 18th century – It just wouldn’t make sense (Unless of course, it’s a time travel story)! This can help you include accurate details about location and even key events. But it is a good idea that during the planning phase, you know the year or even dates the story is set in. ![]() You don’t always have to include the exact date or year in your story. Some stories especially about time travel may be set across multiple time periods. The physical location is also something that can be included at the beginning of the story to set the story’s tone. It is a good idea to explain each new location in great detail, so the readers feel like they are also right there with the characters. For example, the tale of Cinderella takes part in two main locations: Cinderella’s Palace and the Ballroom at the Prince’s Palace. Location is the physical place/s the story takes part in mostly. The easiest element to understand is location. ![]() Settings in stories refer to three things: Location, Time Period and Mood. The only thing that changes is the lessons they learn, and how these impact them.Ĭheck out this post on 20 tips for character development for more guidance. Deep inside their personality should stay more or less the same. But be careful here – Growth should not be mistaken for a personality change! The main character must stay true to who they are. Depending on your plot, they might become a better person, or even a worse one – if this is a villain’s origin story. All the challenges and obstacles they face in the story allow them to learn, grow and develop. The main character also goes through changes throughout the story. You should also provide a hint to what this character’s major conflict is in the story (more on conflict later). While introducing this character it is a good idea to include key information about this character’s personality, past and physical appearance. The main character should be introduced at the beginning. Stories can also have multiple secondary characters, such as supporting characters and villain/s. Every story has at least one main character. CharactersĬharacters are the most familiar element in stories. 5 Elements Of A Storyīelow we have explained each of the five elements of a story in detail, along with examples. You may also notice that these story elements are what most book outlining techniques are based on. These five elements are a great place to start when you need help planning your story. The most universally used story elements contain just five building blocks: In fact, there can be as few as 4 elements in literature all the way up to 12 elements. Over the years, writers have adapted these elements to suit their writing process. By understanding each element, you increase the chances of writing a better story or novel. Simply put, these elements remind writers what to include in stories, and what needs to be planned. Without these blocks, a story will break down, failing to meet the expectations of readers. Story elements are the building blocks needed to make a story work. ![]() Heads up: This post includes affiliate links like Amazon ones, so I. That’s why I recommend buying them with your normal Amazon shopping to get free shipping. Adjustable ears with only elastic (method 1) Adjustable ears with only elastic (method 2) Adjustable ears with fabric straps. ![]() If you’re buying them online, shipping often costs as much as the beads themselves. Kandi Patterns: Over 16000 free pony bead patterns for kandi cuffs, as well as perler bead patterns, kandi tutorials, kandi photos, and an active kandi.These normally come in bulk packs of 50-1000 beads, so if you only need a few it’s a waste. If you enjoyed this equine collection, bookmark it and share it with your friends and fellow crafters. This was created by the Perler bead site so they have a very comprehensive and easy-to-follow tutorial on their website. They’re widely available in craft stores, online shops, and Amazon. These plastic beads come in every color of the rainbow, have fun designs and letters, and some even glow in the dark. To make up for the lack of a pattern for the rocking horse, here is a 3D Carousel. Unlike elastic or fabric ties, you don’t need to worry about fraying.Im making one for my farther-in-laws Christmas. The Youtuber is using regular sized pony beads that kids use for jewelry. Pony bead dragon, combination of 4 different designs, and about 16 hours of trial and error. See more ideas about pony beads, pony bead patterns, pony bead crafts. You’ll need pony beads because they have a hole that’s big enough for elastic. Explore Aaron Laura Downing's board 'Pony Bead Keychain Patterns' on Pinterest. With enough supply to last several projects, the uses of this pony bead assortment are endless.Skip to 5:20 to see how the adjustable ears are made. For camp, scouting, or preschool, these kids pony beads can be used to develop color and shape recognition, fine-tune motor skills, or help with basic math. Mandala Crafts Plastic Pony Beads for Jewelry Making Large Plastic. See more videos about Small Easy Things to Crochet, Mini Perler Bead Patterns. Big Pony Bead Kit for Bracelets Kids Crafts Hair Beads 1200 PCs 9mm Opaque Rainbow. If you love these projects, be sure to subscribe to our newsletter to. Skill levels range from beading patterns for beginners to advanced beading projects. You will find beadwork patterns for necklaces, bracelets, holiday jewelry, and more. Easy Pony Bead Alligator Pattern to make into a key chain. Discover videos related to Easy Pony Bead Star Pattern on TikTok. With this collection of free beading patterns, you can craft your own jewelry to match any outfit or make an impressive gift for any occasion. Add a dab of glue on your knot and the half hitch attachment to the lanyard and let dry. Use a half hitch (see detail below) to secure it to lanyard hook. With just the right amount of sheen, these fancy pony beads with holes will add a playful and charming touch for toddlers, kids, girls, teens, and adults to indulge in. Fold your cord in half to find the center. Pony Bead Patterns (1 - 60 of 467 results) Price () Shipping All Sellers Sort by: Relevancy 90s Bead Lizard Pattern (2.2k) 2.50 Digital Download Add to cart More like this 90s Bead Lizard Knitting Pattern, Lizard Pattern, Knit Toy Pattern, Pony Bead Lizard, 90s Toys (355) 2. The barrel pony beads can be melted to create jazzy bows or elevate a hair braiding project. For crafters or sewing hobbyists, these craft pony beads are handy for a multitude of handiworks, from using as big beads for hair braids to making fashionable shoelaces and cute clips to beading or embellishing banners, textiles, ornaments, animals, and suncatchers. No matter whether they are being used as pony bracelet beads or for making rave, Kandi, or loom paracord bracelets, this craft beads assortment with its practical selection of colors can satisfy any design. ![]() This pretty pony bead set is sure to give you hours of fun. Unlike mixed plastic beads kits, these assorted pony beads are meticulously organized in a sectioned case and are easy to work with, essential for nifty beadwork and intricate pony beads patterns. Things to make with Perler beads: Perler beads come in big buckets and. A dynamic selection of primary colors is represented in this rainbow pony beads set including purple, orange, red, gold, blue, yellow, light blue, white, pink, ivory, black, and lime green. These friendly pony Bead Lizards by Sugar Bee Crafts are a perfect summer camp craft. Drilled to perfection, these plastic pony beads for crafts are simple to string, sew, or thread and can also be glued on various surfaces. With gorgeous and vivid color that will not fade, bleed, or lose sheen, these crafting beads are precisely what you need for pony bead jewelry and crafts. Are you looking to enhance your handmade creations with cool, chic, and colored beads? These pony large beads can be the answer. ![]() This tool will help you generate a professional About Us page for your site, blog, or other online platform. Page maker About Us! We are happy that you are here. It's often a good idea to have a professional writer on your About Us page to make it look professional and represent your brand well. It's many time when the first page potential visitors see when they visit your site, so it's an opportunity to present yourself and build reliability. What is the About Us page? The About Us page is a page on your website that tells you who you are as a company, your history, mission, goals and values. ![]() This page can also be a great place to introduce your team and give visitors the background and experience of the people working on your site. The About Us page is a great way to introduce visitors to your business and better understand who you are and what you do. This About Us page maker is designed the way to help you create an About Us page on your Site. With the About page builder, you can create a page that fits your brand and attracts visitors. The About Us page allows you to share basic information about your business with website visitors. Many users have created amazing About Us pages using our tool. Even If you're building a brand new website or revamping an old one, the About Us page is a great way to introduce your visitors to your company's people, philosophy and history. About Us Page Generator is designed to help people like business owners, entrepreneurs and website managers create professional About Us websites quickly and easily. Welcome to the About Us page maker! We are happy that you are here. ![]() However, subscription is not a must in the game, and users who do not subscribe will still have access to the basic elements in the game. The subscription offers benefits such as removing all ads, unlocking all game packs, having unlimited lives, receiving 2000 coins instantly, and receiving 500 coins and 10 energy per day. The game is free to play, but there is a Diamond Membership subscription service available for $4.99 per week. So these are all AARP free games you can play on PC on a web. The game offers a variety of tasks that will keep you engaged and entertained. puzzles, Medium Sudoku puzzles, Hard Sudoku puzzles, and Expert Sudoku puzzles. You can use the flags you earn to restore and decorate different areas that need to be brought back to their former glory. The object is to reveal a hidden picture by. Here in this article, we are gonna present to you two of the popular Android emulators to use Letras: Aprende a leer sílabas on PC. Numbers cannot repeat within cages, a single row. Each puzzle consists of a blank grid with colored clues on the left of every row and on the top of every column. So even if the official version of Letras: Aprende a leer sílabas for PC not available, you can still use it with the help of Emulators. Make sure the sum of numbers in each cage is equal to the number in the upper left corner of the cage. Pay attention to the cages groups of cells indicated by dotted lines. As a logic puzzle, Sudoku is also an excellent brain game. Fill all rows, columns, and 3x3 blocks with numbers 1-9 exactly like in classic sudoku. ![]() The goal of Sudoku is to fill a 9×9 grid with numbers so that each row, column and 3×3 section contain all of the digits between 1 and 9. Classic sudoku puzzles with different levels you choose: from easy. If you like to raise big sudoku challenges and make your brain work hard, this classic sudoku game is also perfect for you. If you like easy sudoku where you can have fun, enjoy, relax and pass your free time in a pleasant way you will love this game. In addition to the Nonogram game, you can also enjoy the fun of building and decorating. Erase Play Free Sudoku Now Sudoku is one of the most popular puzzle games of all time. Sudoku Puzzles - Classic Fun is your free puzzle game. Sudoku Deluxe is for all players : from beginners to advanced players. The game features many different themes and challenges, making it interesting and engaging. You can use hints and extra lives when you are stuck. More than 500 levels of Sudoku in 4 different styles await Anti-Diagonal, Argyle, Sudoky DG, and Bricks, all solvable with 100 logic no guesswork needed. The game requires you to fill in the grids according to the numbers at the end of the rows and columns. Nonogram Color Sudoku Puzzle is a classic logic picture game that can help train your brain and sharpen your mind. Send shockwaves across the board that break the ice when placing the correct numbers or charms.Softonic review Nonogram Color Sudoku Puzzle - A Classic Logic Picture Game Three (3) unique puzzles a day allow you to collect coins and win badges in Classic, Irregular and now Ice Breaker game mode. If that’s not enough, test your skills in all new Daily Challenges. Looking for a change? Try playing in Irregular mode! The same rules but each block of numbers is in fun and colourful shapes. You may never go back to the classic way of playing again! Play at your own pace with freshly generated puzzles giving you an endless supply of unique Sudoku games.įor more fun, select from four (4) different themes including playing with Charms instead of numbers. Die Funktion, die besonders für mittel schwere Sudoku Spiele hervorzuheben ist, ist die Notizfunktion. Vorteile von Online Sudoku mittel schwer. Wenn Sie Online spielen versuchen Sie es mit analogen Taktiken zur Lösung von mittel schweren Sudoku. Play classic puzzles with six (6) levels of difficulty, offering you just the right amount of challenge. So können Sie Ihre Handlungen zurückverfolgen und ggf. 1 logic puzzle game has turned up the brilliance with fresh colours, exciting new features, new levels of difficulty, daily challenges, achievements and MORE! Keep your mind sharp with hundreds of brain training puzzles for players of all ages! gives you the opportunity to solve killer sudoku for free, receive hints, correct the data, take notes. ![]() Microsoft Sudoku is bringing the classic game you love to a whole new light! The No. Expert Killer Sudoku is suitable for professionals who are aware of all sudoku tricks and techniques. Use our extra and lump sum repayment calculator to see how making extra repayments can reduce your loan amount. You can do this by paying more than the monthly (or fortnightly or weekly) minimum amount. Make extra repaymentsĪn easy way to pay your loan off faster is by making extra repayments into your loan. *The table above assumes an owner occupier loan over a 30-year loan term with a $500,000 loan amount and $10 monthly fees. We’ve used the example home loan from above to demonstrate how a lower interest rate can impact your repayments and overall loan amount. If it’s been a while since you’ve checked your interest rate, you could be paying too much. Getting the lowest possible interest rate is one of the easiest ways to save on your home loan. There are plenty of ways you can save on your mortgage, including: Find a lower interest rate No one wants to spend more money than they need to on anything, including their home loan. How can I pay off my loan faster or save money on my loan? On the other hand, if you choose to only make interest-only repayments, your monthly repayment amounts may be smaller but the overall cost of the loan will be bigger because you’re deferring paying off the amount borrowed. Repayment type: If you choose principal and interest repayments, your monthly loan repayments may be higher but your overall loan costs will be lower, because you’re chipping away at the amount you’ve borrowed as well as the interest portion of the loan. Here’s how your repayments could change with different loan terms. That also means your overall loan amount will be smaller than if you chose a longer loan term.įor example, let’s say you take out a $500,000 loan over a 30-year loan term, making monthly principal and interest repayments with an interest rate of 2.5% p.a. If you chose a shorter loan term, your monthly or fortnightly repayments may be bigger, but you’ll pay less interest over the life of the loan. Loan term: A longer loan term means your monthly repayments will be smaller, but over the total loan term you will actually end up paying more in interest because the interest has more time to accumulate. Other factors, such as the loan term, repayment frequency and type can also have an impact on your repayments. ![]() There are many factors that can have an impact on your repayments, the most obvious ones being the interest rate and the loan amount. How does my loan term, frequency and repayment type impact my repayments? This means whatever interest rate you use will be applied for the whole loan term. While there are many factors that can influence this calculation such as changes in interest rates, a decision to refinance, or using a redraw facility, the calculator will still be able to give you an estimate of how much your regular repayments could be and the total interest paid over the life of the loan.īy changing the interest rate, loan term, and repayment frequency fields, you can compare how these differences can impact your repayments.ĭisclaimer: The results yielded by the calculator assume no changes in interest rates over the loan term. Your Mortgage’s mortgage calculator considers a variety of factors to determine how much your regular repayments will be over the loan term. How does the mortgage repayment calculator work? Different terms, fees or other loan amounts might result in a different comparison rate. ![]() ![]() Warning: this comparison rate is true only for this example and may not include all fees and charges. *The Comparison rate is based on a $150,000 loan over 25 years. Monthly repayments, once the base criteria are altered by the user, will be based on the selected products’ advertised rates and determined by the loan amount, repayment type, loan term and LVR as input by the user/you. All products will list the LVR with the product and rate which are clearly published on the product provider’s website. Some products will be marked as promoted, featured or sponsored and may appear prominently in the tables regardless of their attributes. However, the ‘Compare Home Loans’ table allows for calculations to be made on variables as selected and input by the user. Base criteria of: a $400,000 loan amount, variable, fixed, principal and interest (P&I) home loans with an LVR (loan-to-value) ratio of at least 80%. ![]() For these calculations the lowest energy state of the atoms had to be used. Calculations at the same levels of theory were performed for isolated atoms, which are used as reference for extracting the enthalpy of formation. ![]() The standard G2, G3, G4, 6–10 and CBS-QB3 16,17 methods were used for about 2000 molecules up to 47 atoms, and W1U and W1BD 13 were used for about 650 molecules up to 16 atoms. However, it is not practical for large flexible molecules since the number of accessible conformations increases exponentially with the number of rotatable bonds. 25–29 MS-AS has demonstrated the importance of the multistructural anharmonicity in determining absolute thermodynamic quantities by reproducing the experimental standard entropy for some small molecules such as ethanol and 1-butanol 25 with an uncertainty of about 4 J/mol K. ![]() have developed a method called multistructural approximation (MS-AS) which allows for taking a Boltzmann average on conformational space and for considering the change in rotational partition function from structure to structure hence, rotation is coupled to conformational change. These methods have improved thermochemistry predictions but they were applied to special cases only and the methods are not practical for complex molecules. Other methods have used experimentally obtained anharmonic constants, 22 second-order rotovibrational perturbation theory, 23 or quadratic correction terms 24 to take the effect of anharmonicity into account for prediction of total atomization energy and enthalpy of formation. 20,21 They found that the anharmonic correction mainly affects the entropy and isochorous heat capacity thermodynamics functions, while the anharmonicity related contributions to the enthalpy of formation only amount to a few percent of the total vibrational contribution. 20 They assumed that anharmonicity only needs to be considered for some selected degrees of freedom and described the molecular vibration of silicon hydrides by a set of independent harmonic and anharmonic modes. treated nuclear motions by taking partial asymmetrical internal rotations into account for a number of small carbon and silicon compounds. Several improvements have been suggested to alleviate these shortcomings. 18 Moreover, calculations of absolute thermodynamics such as standard entropy and heat capacity are reported much less often than the enthalpy of formation despite their importance. The empirical corrections limit their predictive capability to the datasets against which they are benchmarked. 2 Methods such as Gaussian-n, 6–10 Weizman-n, 11–15 and Petersson-style complete basis set (CBS) models 16,17 have improved accuracy in ab initio thermochemistry by combining calculations at different levels of theory and basis sets with empirical corrections in most methods. 1–5 Therefore, a large amount of effort has gone into the development of quantum chemical methods to predict thermochemistry, especially enthalpy of formation, based on a theoretical description of molecular electronic structure and nuclear motion. Prediction of thermochemistry is crucial for designing chemicals with new functionality since fundamental properties such as Gibbs free energy, enthalpy, heat capacity, and standard entropy are needed to understand stability and reaction energies of compounds. Finally, in order to facilitate the analysis of thermodynamics properties by others we have implemented a new tool obthermo in the OpenBabel program suite including a table of reference atomization energy values for popular thermochemistry methods. This paper also provides predictions of Δ f H 0, S 0, and C V for well over 700 compounds for which no experimental data could be found in the literature. With the correction we find an RMSD from experiment of ≈13 J/mol K for 1273 compounds. This allows an empirical correction of the calculated entropy for molecules with multiple conformations. We observe that the deviation of composite quantum thermochemistry recipes from experimental S 0 corresponds roughly to the Boltzmann equation ( S = RlnΩ), where R is the gas constant and Ω the number of possible conformations. This problem can be tackled in principle by performing thermochemistry calculations for all stable conformations, but this is not practical for large molecules. Quantum methods systematically underestimate S 0 for flexible molecules in the gas phase if only a single (minimum energy) conformation is taken into account. ![]() A large data set may help to evaluate quantum thermochemistry tools in order to uncover possible hidden shortcomings and also to find experimental data that might need to be reinvestigated, indeed we list and annotate approximately 200 problematic thermochemistry measurements. Large scale quantum calculations for molar enthalpy of formation (Δ f H 0), standard entropy ( S 0), and heat capacity ( C V) are presented. |
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