Survey of main group compounds (HBr) at the Gaussian-4 level of theory: Adiabatic ionization energies and enthalpies of formation

Rayne, Sierra; Forest, Kaya

doi:10.1016/j.comptc.2011.07.033

Cited by 18 publications

(13 citation statements)

References 255 publications

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“…For AlF 3 , LiF and KH we have to bear in mind that the experimental value for a vertical transition was not available, therefore geometry relaxations may explain the mismatch. This is only partially true for KH, where the inclusion of adiabatic effects in the perturbative calculations still leaves a sizable disagreement (∼2 eV) [146]; in this case it is not completely unreasonable to call for a further assessment of the experimental value.…”

Section: Comparison To Experimentsmentioning

confidence: 99%

GW100: A Plane Wave Perspective for Small Molecules

Maggio

Liu

Setten

et al. 2017

J. Chem. Theory Comput.

154

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In a recent work, van Setten and co-workers have presented a carefully converged GW study of 100 closed shell molecules [ J. Chem. Theory Comput. 2015 , 11 , 5665 - 5687 ]. For two different codes they found excellent agreement to within a few 10 meV if identical Gaussian basis sets were used. We inspect the same set of molecules using the projector augmented wave method and the Vienna ab initio simulation package (VASP). For the ionization potential, the basis set extrapolated plane wave results agree very well with the Gaussian basis sets, often reaching better than 50 meV agreement. In order to achieve this agreement, we correct for finite basis set errors as well as errors introduced by periodically repeated images. For positive electron affinities differences between Gaussian basis sets and VASP are slightly larger. We attribute this to larger basis set extrapolation errors for the Gaussian basis sets. For quasi particle (QP) resonances above the vacuum level, differences between VASP and Gaussian basis sets are, however, found to be substantial. This is tentatively explained by insufficient basis set convergence of the Gaussian type orbital calculations as exemplified for selected test cases.

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Section: Comparison To Experimentsmentioning

confidence: 99%

GW100: A Plane Wave Perspective for Small Molecules

Maggio

Liu

Setten

et al. 2017

J. Chem. Theory Comput.

154

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“…In previous work, [15][16][17][18][19][34][35][36][37][38][39][40][41][42][43][44][45][46][47] the G4MP2, G4, and W1BD levels of theory have been shown to yield chemically accurate thermodynamic data on a broad range of inorganic and organic compounds. To confirm the accuracy of these theoretical methods, we also compared our calculated f H • (g) for ammonia (NH 3 ), hypochlorous acid (HOCl), and water (H 2 O) to the corresponding experimental values from the NIST database.…”

Section: Resultsmentioning

confidence: 99%

Thermodynamic properties of chloramine formation and related reactions during water treatment: A G4MP2, G4, and W1BD theoretical study

Rayne¹,

Forest

2014

Journal of Environmental Science and Health, Part A

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A high-level gas and aqueous phase theoretical thermodynamic study was conducted on the primary and related chemical reactions which occur during chloramination for water treatment using the G4MP2, G4, and W1BD composite methods with the SMD, PCM, and CPCM solvation models. The standard state (298.15 K, 1 atm or 1M) formation of mono-, di-, and tri-chloramines from their precursors via hypochlorous acid chlorination is substantially exothermic and exergonic in both the gas and aqueous phases. The excellent agreement between experimental and theoretical values for a range of structural and thermodynamic calculations on a suite of calibration compounds suggests that the G4MP2, G4, and W1BD calculations meet or exceed criteria for thermochemical accuracy. The temperature influence on the thermodynamics of chloramine formation is projected to be negligible regardless of phase between 0 and 100°C. Additional thermodynamic calculations were undertaken on associated chloramination reactions involving the disproportionation of monochloramine, the decomposition of di- and tri-chloramine, and the reactions of trichloramine with ammonia and dichloramine. The results from these investigations not only provide a better understanding of the reaction thermodynamics, they also allow for a more rigorous interpretation of proposed chloramination mechanisms.

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“…The enthalpies of formation (kJ/mol) for CH 3 , SH, and CF 3 , at 298 K are established as 147, 139.3, and –470.3. For CH 3 SH, we adopt the NIST value of –22.8 kJ/mol that is intermediate between recently computed values of –23.8 and –21.6 and for CF 3 SH we select the mean of –650.7 kJ/mol from [38] (–653.1) and [39] (–648.3). These enthalpies of formation at 298 K give –309.1 and –319.7 kJ/mol as the enthalpy change for reactions and , respectively, and we adopt the mean value, –314 kJ/mol, as the enthalpy change for reaction .…”

Section: Calculated Resultsmentioning

confidence: 99%

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF₂ClSH

Rossabi

Smith

Heard

et al. 2015

Int J of Chemical Kinetics

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Chemically activated CF 3 SH, CFCl 2 SH, and CF 2 ClSH were formed through combination of SH and CF 3 , CFCl 2 , and CF 2 Cl radicals, respectively. The SH radical was prepared by abstraction of an H-atom from H 2 S by the halocarbon radical produced during photolysis of (CF 3 ) 2 C=O, (CFCl 2 ) 2 C=O, or (CF 2 Cl) 2 C=O. 1,2-HX (X = F, Cl) elimination reactions were observed from CF 3 SH, CFCl 2 SH, and CF 2 ClSH with products detected by GC-MS. The combination reaction of CF 2 Cl radicals with SH radicals prepared CF 2 ClSH molecules with approximately 318 kJ/mol of internal energy. The experimental rate constants for elimination of HCl and HF from CF 2 ClSH were 3 ± 3 × 10 10 and 2 ± 1 × 10 9 s −1 , respectively. Comparison to Rice-Ramsperger-Kassel-Marcus (RRKM) calculated rate constants assigned the threshold energies as 171 ± 12 and 205 ± 12 kJ/mol for the unimolecular elimination of HCl and HF, respectively. Theoretical calculations using the B3PW91, MP2, and M062X methods with the 6311+G(2d,p) and 6-31G(d',p') basis sets established that for a specific method the threshold energies differ by only 4 kJ/mol between the two different basis sets. There was wide variation among the three methods, but the M062X approach appeared to give threshold energies closest to the experimental values. Chemically activated CF 3 SH and CFCl 2 SH were also prepared with about 318 kcal mol −1 of internal energy, and the HX (X = F, Cl) elimination reactions were observed. Only HCl loss was detected from CFCl 2 SH, but the rate was too fast to measure with our kinetic method; however, based on our detection limit the HF elimination channel is at least 50 times slower. C

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Survey of main group compounds (HBr) at the Gaussian-4 level of theory: Adiabatic ionization energies and enthalpies of formation

Cited by 18 publications

References 255 publications

GW100: A Plane Wave Perspective for Small Molecules

GW100: A Plane Wave Perspective for Small Molecules

Thermodynamic properties of chloramine formation and related reactions during water treatment: A G4MP2, G4, and W1BD theoretical study

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF₂ClSH

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Survey of main group compounds (HBr) at the Gaussian-4 level of theory: Adiabatic ionization energies and enthalpies of formation

Cited by 18 publications

References 255 publications

GW100: A Plane Wave Perspective for Small Molecules

GW100: A Plane Wave Perspective for Small Molecules

Thermodynamic properties of chloramine formation and related reactions during water treatment: A G4MP2, G4, and W1BD theoretical study

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF2ClSH

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Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF₂ClSH