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Theoretical chemistry: current applications to photochemistry and thermochemistry

Ornellas, Fernando R.
Fonte: SPRINGER; NEW YORK Publicador: SPRINGER; NEW YORK
Tipo: Artigo de Revista Científica
ENG
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A historical perspective is given contrasting challenges and advances in theoretical chemistry at the time the first issue of Theoretical Chemistry Accounts appeared in 1962 and the progress achieved since then as expressed in current state-of-the-art applications in photochemistry and thermochemistry.

Sintese, caracterização e termoquimica de materiais lamelares nanoestruturados derivados de magadeita; Synthesis, characterization and thermochemistry of nanostructured lamellar materiais derivative of magadiite

Giovanni Cavichioli Petrucelli
Fonte: Biblioteca Digital da Unicamp Publicador: Biblioteca Digital da Unicamp
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 22/02/2008 PT
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O composto lamelar magadeíta foi hidrotérmicamente sintetizado na forma (Na2Si14O29.9H2O) [Namag], que ao ser tratado com HCl 0.10 mol dm gerou [Hmag]. O nanocomposto hidratado ácido silícico lamelar magadeíta [Hmag] (H2Si14O29.2H2O), foi utilizado na intercalação de alquilaminas polares de fórmula geral H3C(CH2)nNH2 (n=1-6) em solução aquosa. A distância interlamelar (d) original da [Hmag] de 1150 pm, apresenta aumento com a intercalação, dando correlações com o número de átomos carbonos da amina alifática (nc): d = [(1313±15) + 20±3)]nc. A quantidade de amina intercalada (Ns) diminui com o aumento de nc: Ns = [(5,87±0,12) ? (0,43±0,03)]nc. Os resultados de titulação calorimétrica deram correlações termodinâmicas com a entalpia: DintH = -[(24,45±0,49) ? (1,91±0,10)]nc e d = [(1576±16) ? (11±1)]DintH. Os valores negativos da energia livre de Gibbs e positivos para entropia deram as correlações: DintG = -[(22,3±0,2) ? (0,5±0,1)]nc and DintS = [(6±1) + (5±1)]nc, respectivamente. A forma ácida [Hmag] foi modificada quimicamente com [3- aminopropiltrimetoxissilano (1N), N-3-trimetoxissililpropiletilenodiamina (2N), N-3-trimetoxissililpropiletilenotriamina (3N) e 3-mercaptopropiltrimetoxissilano (1S)]. Os materiais sintetizados foram caracterizados por difração de raios-X...

Síntese e termoquímica de adutos de brometos de metais bivalentes com aminas hetrocíclicas; Synthesis and thermochemistry of the adducts of bivalent transition metal bromides with heterocyclic amines

Abdul Majeed Khan
Fonte: Biblioteca Digital da Unicamp Publicador: Biblioteca Digital da Unicamp
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 07/03/2013 PT
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Os adutos MX2.nL (M = Mn, Fe, Co, Ni, Cu ou Zn, L = 3-cianopiridina, piperidina ou piperazaina, X = Br, n = 0,5, 0,75, 1, 1,5, 2 ou 4), foram sintetizados e caracterizados através de análise elementar, determinação de pontos de fusão, espectroscopia IV e eletrônica e análise termogravimétrica. Todos os adutos são sólidos e sensíveis à umidade atmosférica. Os dados espectroscópicos na região do infravermelho, para os adutos, indicam a presença de um mesmo padrão de bandas em comparação com os respectivos ligantes livres. No entanto, deslocamentos de algumas bandas são evidentes devido à coordenação dos íons metálicos aos ligantes. As entalpias de dissolução em HCl 1,2 molL dos adutos, brometos metálicos e ligantes, foram determinados. Através de ciclos termoquímicos apropriados, foram calculadas as variações de entalpia padrão para as reações: MBr2 (s) + nL (s,l)  MBr2.nL (s) DrH MBr2.nL (s) MBr2 (s) + nL (g) DDH MBr2 (g) + nL (g)  MBr2.nL (s) DMH Foram também calculadas as variações entálpicas padrão de formação dos adutos e as variações entálpicas padrão da ligação metal-nitrogênio. Os parâmetros termoquímicos permitiram determinar a ordem de acidez dos adutos: para os adutos de ligante 3-cianopiridina: NiBr2>FeBr2> CoBr2>MnBr2 e ZnBr2>CuBr2...

Termoquímica na Unicamp: depoimento sobre uma jornada de 25 anos

Chagas,Aécio Pereira; Airoldi,Claudio
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/06/1999 PT
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This article describes the progress of a group of investigation on thermochemistry, which started in 1972. A homemade calorimeter was employed to provide quantitative support to the information on interative effect between lanthanide cations and halides or pseudohalides, in non-aqueous solvents, previously derived from conductometric titrations. However, the features of this instrument were not able to detect the thermal effects. Therefore, the great input to the group came from the acquisition of an LKB commercial apparatus, by the University in 1975. Considering the historical development of the coordination chemistry in Brazil, which was previously dedicated to strutural features of adducts, without focusing the energetic envolved in any coordinationcompound. Since starting the thermochemistry study, numerous masters and doctoral thesis covering more than a hundred adducts and a reasonable number of chelates, were presented systematizing data in order to understand the behavior of this kind of coordination compounds (C. Airoldi and A. P. Chagas, Coord. Chem. Rev. 1992, 119, 29). This knowledge enabled an extension of the study to include some heterogeneous systems formed by natural or synthetic materials like immobilized silica gel...

Do termoscópio ao termômetro digital: quatro séculos de termometria

Pires,Denise Prazeres Lopes; Afonso,Júlio Carlos; Chaves,Francisco Artur Braun
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/12/2006 PT
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This work describes the evolution of temperature measurement in the last four centuries using thermometers based on the thermal expansion of liquids such as ethyl alcohol and mercury. The concept of temperature was strongly dependent on the researcher and there was no systematic temperature scale for universal use. The precursor of the common thermometer was the thermoscope, probably invented at the end of the XVIth century. In the XVIIIth century the instrument was greatly improved and several thermometric scales were proposed some of which have been in use until now. These scales were based on arbitrary points. Mercury and ethyl alcohol were the most employed thermometric fluids. In the XIXth century, the concept of absolute zero was a great advance in this field. The most important contribution during the XXth century was the establishment of international temperature scales. The design of the thermometer has been essentially the same along the last 300 years, but many models were proposed for industrial and research purposes. Its association with the densimeter was of great importance for control of industrial chemical processes and also for teaching purposes in the past. Nowadays, there is a clear tendency to replace mercury-based thermometers by electronic digital models. Thermochemistry is the natural relationship between temperature and chemistry.

Surprisingly Long-Lived Ascorbyl Radicals in Acetonitrile: Concerted Proton-Electron Transfer Reactions and Thermochemistry

Warren, Jeffrey J.; Mayer, James M.
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
EN
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Proton-coupled electron transfer (PCET) reactions and thermochemistry of 5,6-isopropylidene ascorbate (iAscH−) have been examined in acetonitrile solvent.iAscH− is oxidized by 2,4,6-tBu3C6H2O• and by excess TEMPO• to give the corresponding 5,6-isopropylidene ascorbyl radical anion (iAsc•−), which persists for hours at 298 K in dry MeCN solution. The stability of iAsc•− is surprising in light of the transience of the ascorbyl radical in aqueous solutions, and is due to the lack of the protons needed for radical disproportionation. A concerted proton-electron transfer (CPET) mechanism is indicated for the reactions of iAscH−. Redox potential, pKa and equilibrium measurements define the thermochemical landscape for 5,6-isopropylidene ascorbic acid and its derivatives in MeCN. These measurements give an O–H bond dissociation free energy (BDFE) for iAscH−of 65.4 ± 1.5 kcal mol−1 in MeCN. Similar studies on underivatized ascorbate indicate a BDFE of 67.8 ± 1.2 kcal mol−1. These values are much lower than the aqueous BDFE for ascorbate of 74.0 ± 1.5 kcal mol−1 derived from reported data.

Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics

Zhang, Ying; Xu, Xin; Goddard, William A.
Fonte: National Academy of Sciences Publicador: National Academy of Sciences
Tipo: Artigo de Revista Científica
EN
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We develop and validate a density functional, XYG3, based on the adiabatic connection formalism and the Görling–Levy coupling-constant perturbation expansion to the second order (PT2). XYG3 is a doubly hybrid functional, containing 3 mixing parameters. It has a nonlocal orbital-dependent component in the exchange term (exact exchange) plus information about the unoccupied Kohn–Sham orbitals in the correlation part (PT2 double excitation). XYG3 is remarkably accurate for thermochemistry, reaction barrier heights, and nonbond interactions of main group molecules. In addition, the accuracy remains nearly constant with system size.

A Hierarchy of Homodesmotic Reactions for Thermochemistry

Wheeler, Steven E.; Houk, Kendall N.; Schleyer, Paul v. R.; Allen, Wesley D.
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em 25/02/2009 EN
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Chemical equations that balance bond types and atom hybridization to different degrees are often used in computational thermochemistry, for example, to increase accuracy when lower levels of theory are employed. We expose the widespread confusion over such classes of equations and demonstrate that the two most widely used definitions of “homodesmotic” reactions are not equivalent. New definitions are introduced and a consistent hierarchy of reaction classes (RC1 – RC5) for hydrocarbons is constructed: isogyric (RC1) ⊇ isodesmic (RC2) ⊇ hypohomodesmotic (RC3) ⊇ homodesmotic (RC4) ⊇ hyperhomodesmotic (RC5). Each of these successively conserves larger molecular fragments. The concept of isodesmic bond separation reactions is generalized to all classes in this hierarchy, providing a unique sectioning of a given molecule for each reaction type. Several ab initio and density functional methods are applied to the bond separation reactions of 38 hydrocarbons containing five or six carbon atoms. RC4 and RC5 reactions provide bond separation enthalpies with errors consistently less than 0.4 kcal mol−1 across a wide range of theoretical levels, performing significantly better than the other reaction types and far superior to atomization routes. Our recommended bond separation reactions were demonstrated by determining the enthalpies of formation (at 298 K) of 1...

Thermochemistry and Molecular Structure of a Remarkable Agostic Interaction in a Heterobifunctional Ruthenium-Boron Complex

Conley, Brian L.; Williams, Travis J.
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em 17/02/2010 EN
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A boron-pendant ruthenium species forms a unique agostic methyl bridge between the boron and ruthenium atoms in the presence of a ligating solvent, acetonitrile. NMR inversion-recovery experiments enable measurement of the activation and equilibrium thermochemistry for formation of the agostic bridge. The mechanism for bridge formation involves displacement of an acetonitrile ligand; thus, this is a rare example of a case where an agostic C—H ligand competitively displaces another tight-binding ligand from a coordinatively saturated complex. Characterization of this complex gives unique insights into development of C—H activation catalysis based on this ligand-metal bifunctional motif.

Thermochemistry of Non-Covalent Ion–Molecule Interactions

Armentrout, P. B.; Rodgers, M. T.
Fonte: The Mass Spectrometry Society of Japan Publicador: The Mass Spectrometry Society of Japan
Tipo: Artigo de Revista Científica
EN
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The thermochemistry of non-covalent ion–molecule complexes has been examined by measuring quantitative bond dissociation energies using threshold collision-induced dissociation in guided ion beam tandem mass spectrometers (GIBMS). The methods used are briefly reviewed and several examples of the types of information and insight that can be obtained from such thermodynamic information are discussed. The hydration of metal cations, both singly and doubly charged, is reviewed and the trends elucidated, mainly on the basis of electrostatic contributions. The binding of alkali metal cations to amino acids has been examined for a range of systems, with both the overall polarizability of the amino acid and the local dipole moment of heteroatomic side-chains shown to be important contributors. The gas-phase interactions of the 12-crown-4 (12C4) polyether with alkali metal cations, classic molecular recognition systems in solution, have been newly compared to previous GIBMS work. These results validate the previous hypothesis that excited conformers were present for Rb+(12C4) and Cs+(12C4) and offer clues as to how and why they are formed.

The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

Hansen, Andreas; Bannwarth, Christoph; Grimme, Stefan; Petrović, Predrag; Werlé, Christophe; Djukic, Jean-Pierre
Fonte: Blackwell Publishing Ltd Publicador: Blackwell Publishing Ltd
Tipo: Artigo de Revista Científica
EN
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Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies were measured by isotherm titration calorimetry (ITC) and theoretically ‘back-corrected’ to yield 0 K gas-phase reaction energies (ΔE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source of error in theoretical thermochemistry protocols. The (‘back-corrected’) experimental reaction energies were used to benchmark (dispersion-corrected) density functional and wave function theory methods. Particularly, we investigated whether the atom-pairwise D3 dispersion correction is also accurate for transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important long-range electron correlation contributions. Both...

Liquid hot NAGMA cooled to 0.4 K: Benchmark thermochemistry of a gas-phase peptide

Leavitt, C.M.; Moore, K.B.; Raston, P.L.; Agarwal, J.; Moody, G.H.; Shirley, C.C.; Schaefer, H.F.; Douberly, G.E.
Fonte: American Chemical Society Publicador: American Chemical Society
Tipo: Artigo de Revista Científica
Publicado em //2014 EN
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Vibrational spectroscopy and helium nanodroplet isolation are used to determine the gas-phase thermochemistry for isomerization between conformations of the model dipeptide, N-acetylglycine methylamide (NAGMA). A two-stage oven source is implemented to produce a gas-phase equilibrium distribution of NAGMA conformers, which is preserved when individual molecules are captured and cooled to 0.4 K by He nanodroplets. With polarization spectroscopy, the IR spectrum in the NH stretch region is assigned to a mixture of two conformers having intramolecular hydrogen bonds composed of either five- or seven-membered rings, C5 and C7, respectively. The C5 to C7 interconversion enthalpy and entropy, obtained from a van't Hoff analysis, are -4.52 ± 0.12 kJ/mol and -12.4 ± 0.2 J/(mol · K), respectively. The experimental thermochemistry is compared to high-level electronic structure theory computations.; Christopher M. Leavitt, Kevin B. Moore III, Paul L. Raston, Jay Agarwal, Grant H. Moody, Caitlyne C. Shirley, Henry F. Schaefer III, and Gary E. Douberly

G3-RAD and G3X-RAD: Modified Gaussian-3 (G3) and Gaussian-3X (G3X) procedures for radical thermochemistry

Henry, David J.; Sullivan, Michael B.; Radom, Leo
Fonte: American Institute of Physics (AIP) Publicador: American Institute of Physics (AIP)
Tipo: Artigo de Revista Científica
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The G3-RAD, G3X-RAD, G3(MP2)-RAD, and G3X(MP2)-RAD, procedures, designed particularly for the prediction of reliable thermochemistry for free radicals, are formulated and their performance assessed using the G2/97 test set. The principal features of the RAD procedures include (a) the use of B3-LYP geometries and vibrational frequencies (in place of UHF and UMP2), including the scaling of vibrational frequencies so as to reproduce ZPVEs, (b) the use of URCCSD(T) [in place of UQCISD(T)] as the highest-level correlation procedure, and (c) the use of RMP (in place of UMP) to approximate basis-set-extension effects. G3-RAD and G3X-RAD are found to perform well overall with mean absolute deviations (MADs) from experiment of 3.96 and 3.65 kJ mol⁻¹, respectively, compared with 4.26 and 4.02 kJ mol⁻¹ for standard G3 and G3X. G3-RAD and G3X-RAD successfully predict heats of formation with MADs of 3.68 and 3.11 kJ mol⁻¹, respectively (compared with 3.93 and 3.60 kJ mol⁻¹ for standard G3 and G3X), and perform particularly well for radicals with MADs of 2.59 and 2.50 kJ mol⁻¹, respectively (compared with 3.51 and 3.18 kJ mol⁻¹ for standard G3 and G3X). The G3(MP2)-RAD and G3X(MP2)-RAD procedures give acceptable overall performance with mean absolute deviations from experiment of 5.17 and 4.92 kJ mol⁻¹...

Experimentação em quimica : alternativas para a termoquimica no ensino medio; Experimental in chemistry : alternatives for teaching thermochemistry in the high school

João Rogerio Miraldo
Fonte: Biblioteca Digital da Unicamp Publicador: Biblioteca Digital da Unicamp
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 25/02/2008 PT
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Experimentação em química: alternativas para a termoquímica no ensino médio. Este trabalho fornece situações experimentais para o ensino de termoquímica no nível médio como forma alternativa para se trabalhar esse conteúdo, além de um texto com a base teórica que sustenta o assunto. A metodologia partiu da análise de uma série de livros didáticos e materiais apostilados de escolas tradicionais de destaque no mercado livreiro. Os experimentos desenvolvidos foram testados com rigor científico e adaptados para o ensino médio. Um termistor foi utilizado como sensor de Temperatura e é a ferramenta fundamental no desenvolvimento dos experimentos. Na concepção desse material alguns aspectos foram relevantes: os conteúdos presentes nos programas oficiais de ensino de química em nível estadual e federal e nos materiais didáticos; materiais de fácil acesso e de baixo custo que viabilizem seu uso em escolas públicas; experimentos que fundamentem conceitos importantes em termoquímica. Os resultados experimentais mostraram-se dentro dos esperados pela literatura, com boa reprodutibilidade e são apresentados para permitir uma análise crítica dos possíveis valores a serem obtidos pelos alunos, bem como os erros, incertezas e aproximações necessárias. Os experimentos não necessitam de instrumentação sofisticada como balanças analíticas e foram desenvolvidos para materiais de fácil acesso. Não geram resíduos químicos perigosos e não envolvem periculosidade.; Experimentation in chemistry: alternatives for teaching thermochemistry in the high school. This work supplies experimental situations for teaching thermochemistry in high school as a alternative way to present this subject in addition to theoretical base related to the subject. The work beguins with the analysis of a significant number of traditional and commercially expressives text books suitable for the high school concerning to the main subject. The developed experiments were tested in chemical laboratory bench with scientific rigor and were adapted for the actual conditions of Brazilian schools. A termistor used as a temperature sensor is the fundamental tool in the development of the experiments. The official programs of teaching of chemistry...

Photochemistry in Terrestrial Exoplanet Atmospheres III: Photochemistry and Thermochemistry in Thick Atmospheres on Super Earths and Mini Neptunes

Hu, Renyu; Seager, Sara
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 05/01/2014
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Some super Earths and mini Neptunes will likely have thick atmospheres that are not H2-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H2-dominated atmospheres and non-H2-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO2 rather than CH4 or CO in a H2-depleted water-dominated thick atmosphere, and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to formation of unsaturated hydrocarbons (C2H2 and C2H4). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b like planets we find that (1) C2H2 features at 1.0 and 1.5 micron in transmission and C2H2 and C2H4 features at 9-14 micron in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general...

W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions

Karton, Amir; Rabinovich, Elena; Martin, Jan M. L.; Ruscic, Branko
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 11/08/2006
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In an attempt to improve on our earlier W3 theory [J. Chem. Phys. {\bf 120}, 4129 (2004)] we consider such refinements as more accurate estimates for the contribution of connected quadruple excitations ($\hat{T}_4$), inclusion of connected quintuple excitations ($\hat{T}_5$), diagonal Born-Oppenheimer corrections (DBOC), and improved basis set extrapolation procedures. Revised experimental data for validation purposes were obtained from the latest version of the ATcT (Active Thermochemical Tables) Thermochemical Network. We found that the CCSDTQ$-$CCSDT(Q) difference converges quite rapidly with the basis set, and that the formula 1.10[CCSDT(Q)/cc-pVTZ+CCSDTQ/cc-pVDZ$-$CCSDT(Q)/cc-pVDZ] offers a very reliable as well as fairly cost-effective estimate of the basis set limit $\hat{T}_4$ contribution. The largest $\hat{T}_5$ contribution found in the present work is on the order of 0.5 kcal/mol (for ozone). DBOC corrections are significant at the 0.1 kcal/mol level in hydride systems. . Based on the accumulated experience, a new computational thermochemistry protocol for first-and second-row main-group systems, to be known as W4 theory, is proposed. Our W4 atomization energies for a number of key species are in excellent agreement (better than 0.1 kcal/mol on average...

W1 and W2 Theories, and Their Variants: Thermochemistry in the kJ/mol Accuracy Range

Martin, Jan M. L.; Parthiban, S.
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 01/11/2005
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In this 2nd chapter of the book Quantum Mechanical Prediction of Thermochemical Data" (ed. Jerzy Cioslowski, Kluwer, 2001; ISBN 0-7923-7077-5), we review the nonempirical computational thermochemistry methods W1 and W2 theory and their variants. The chapter is made available online following a change in publisher E-print policy.; Comment: 32 pages: differs only in minor formatting details from published book chapter. Posted online following purchase of Kluwer by Springer and move to "Romeo Green" policy

W3 theory: robust computational thermochemistry in the kJ/mol accuracy range

Boese, A. Daniel; Oren, Mikhal; Atasoylu, Onur; Martin, Jan M. L.; Kallay, Mihaly; Gauss, Juergen
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 14/11/2003
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We are proposing a new computational thermochemistry protocol denoted W3 theory, as a successor to W1 and W2 theory proposed earlier [Martin and De Oliveira, J. Chem. Phys. 111, 1843 (1999)]. The new method is both more accurate overall (error statistics for total atomization energies approximately cut in half) and more robust (particularly towards systems exhibiting significant nondynamical correlation) than W2 theory. The cardinal improvement rests in an approximate account for post-CCSD(T) correlation effects. Iterative T_3 (connected triple excitations) effects exhibit a basis set convergence behavior similar to the T_3 contribution overall. They almost universally decrease molecular binding energies. Their inclusion in isolation yields less accurate results than CCSD(T) nearly across the board: it is only when T_4 (connected quadruple excitations) effects are included that superior performance is achieved. $T_4$ effects systematically increase molecular binding energies. Their basis set convergence is quite rapid, and even CCSDTQ/cc-pVDZ scaled by an empirical factor of 1.2532 will yield a quite passable quadruples contribution. The effect of still higher-order excitations was gauged for a subset of molecules (notably the eight-valence electron systems): T_5 (connected quintuple excitations) contributions reach 0.3 kcal/mol for the pathologically multireference X ^1\Sigma^+_g state of C_2 but are quite small for other systems. A variety of avenues for achieving accuracy beyond that of W3 theory were explored...

Benchmark thermochemistry of the C_nH_{2n+2} alkane isomers (n=2--8) and performance of DFT and composite ab initio methods for dispersion-driven isomeric equilibria

Karton, Amir; Gruzman, David; Martin, Jan M. L.
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 20/05/2009
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The thermochemistry of linear and branched alkanes with up to eight carbons has been reexamined by means of W4, W3.2lite and W1h theories. `Quasi-W4' atomization energies have been obtained via isodesmic and hypohomodesmotic reactions. Our best atomization energies at 0 K (in kcal/mol) are: 1220.04 n-butane, 1497.01 n-pentane, 1774.15 n-hexane, 2051.17 n-heptane, 2328.30 n-octane, 1221.73 isobutane, 1498.27 isopentane, 1501.01 neopentane, 1775.22 isohexane, 1774.61 3-methylpentane, 1775.67 diisopropyl, 1777.27 neohexane, 2052.43 isoheptane, 2054.41 neoheptane, 2330.67 isooctane, and 2330.81 hexamethylethane. Our best estimates for $\Delta H^\circ_{f,298K}$ are: -30.00 n-butane, -34.84 n-pentane, -39.84 n-hexane, -44.74 n-heptane, -49.71 n-octane, -32.01 isobutane, -36.49 isopentane, -39.69 neopentane, -41.42 isohexane, -40.72 3-methylpentane, -42.08 diisopropyl, -43.77 neohexane, -46.43 isoheptane, -48.84 neoheptane, -53.29 isooctane, and -53.68 hexamethylethane. These are in excellent agreement (typically better than 1 kJ/mol) with the experimental heats of formation at 298 K obtained from the CCCBDB and/or NIST Chemistry WebBook databases. However, at 0 K a large discrepancy between theory and experiment (1.1 kcal/mol) is observed for only neopentane. This deviation is mainly due to the erroneous heat content function for neopentane used in calculating the 0 K CCCBDB value. The thermochemistry of these systems...

W4 thermochemistry of P_2 and P_4. Is the CODATA heat of formation of phosphorus atom correct?

Karton, Amir; Martin, Jan M. L.
Fonte: Universidade Cornell Publicador: Universidade Cornell
Tipo: Artigo de Revista Científica
Publicado em 28/06/2007
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The high-accuracy W4 computational thermochemistry protocol, and several post-W4 methods, have been applied to the P$_2$ and P$_4$ molecules. Contrary to previous studies, we find the experimental thermochemistry to be fundamentally sound. The reaction enthalpy for P$_4\to 2$P$_2$ has a very significant contribution from post-CCSD(T) correlation effects. We derive a gas-phase heat of formation for the phosphorus atom of $\Delta H^\circ_{f,0}$[P(g)]=75.54$\pm$0.1 kcal/mol and $\Delta H^\circ_{f,298}$[P(g)]=75.74$\pm$0.1 kcal/mol, in the upper half of the CODATA uncertainty interval.; Comment: Mol. Phys., in press (Peter Pulay issue)