A study of vibrational anharmonicity, fermi resonance interactions, and local mode behavior in CH3Cl

Duncan, J.L.; Law, Mark M.

doi:10.1016/0022-2852(90)90003-9

Cited by 68 publications

(16 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is the most significant difference between the PES(F,Cl) and CCSD(T) geometries. As shown in Table , there is also good agreement between the PES(F,Cl) vibrational frequencies and the ab initio and experimental , values. The comparison in Table is with the CEPA-1 frequencies, since frequencies for only the symmetric modes were determined in the CCSD(T) calculations.…”

Section: Pes(fcl) Analytic Potentialsupporting

confidence: 70%

See 1 more Smart Citation

Trajectory Studies of S_N2 Nucleophilic Substitution. 7. F^- + CH₃Cl → FCH₃ + Cl^-

Wang

Hase

1998

J. Phys. Chem. A

View full text Add to dashboard Cite

The PES(F,Cl) analytic potential energy surface, developed previously, is used in a trajectory study of the F- + CH3Cl SN2 reaction. The trajectory SN2 rate constants, as a function of reactant relative translational energy E rel and CH3Cl temperature, are in good overall agreement with the experimental rate constants and those calculated using an ion−molecule capture/RRKM statistical model applied to PES(F,Cl). The latter agreement exists even though the reaction dynamics is decidedly nonstatistical. For high E rel the reaction is direct. At lower E rel there is evidence for formation of an ion−molecule complex; however, its lifetime is too short for complete energy randomization to occur. The velocity scattering angle is isotropic at low E rel but becomes anisotropic with forward scattering as E rel is increased. The reaction exothermicity is primarily partitioned to product vibration, in disagreement with a previous experimental study. Energy transfer from the reactants to products is very selective. Excess reactant relative translational energy almost exclusively goes to product relative translation. Similarly, C−Cl stretch excitation goes to product vibration. For a 300 K CH3Cl rotational temperature, the total angular momentum is dominated by the reactant orbital angular momentum, which is strongly correlated with the product orbital angular momentum.

show abstract

Section: Pes(fcl) Analytic Potentialsupporting

confidence: 70%

“…c Calculations from ref , with a basis of 169 cGTOs, roughly equivalent to the 6-311+G** basis. d The experimental CH 3 Cl and CH 3 F harmonic frequencies are from refs and , respectively.…”

Section: Pes(fcl) Analytic Potentialmentioning

confidence: 99%

Trajectory Studies of S_N2 Nucleophilic Substitution. 7. F^- + CH₃Cl → FCH₃ + Cl^-

Wang

Hase

1998

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…The 2ν 5 (E) and 2ν 3 + ν 5 (E) levels presented in Ref. 45 are lower by around 3 and 5 cm −1 , respectively, when compared with new values measured in Ref. 8.…”

Section: B Vibrational J = 0 Energiesmentioning

confidence: 47%

“…8 In the comparison against values reported in Ref. 45, and subsequently used in Ref. 47, we exercise some caution.…”

Section: B Vibrational J = 0 Energiesmentioning

confidence: 96%

Accurate ab initio vibrational energies of methyl chloride

Owens

Yurchenko

Yachmenev

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level ab initio theory for the two main isotopologues of methyl chloride, CH3 (35)Cl and CH3 (37)Cl. The respective PESs, CBS-35( HL), and CBS-37( HL), are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY 3Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35( HL) and CBS-37( HL) PESs reproduce the fundamental term values with root-mean-square errors of 0.75 and 1.00 cm(-1), respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH3Cl without empirical refinement of the respective PESs.

show abstract

“…For the 35 ZPEs needed, Martin and de Olivera [32] were the source of 28 experimental ZPEs and 7 additional experimental ZPEs were obtained from other sources. The latter were for C 2 H 6 [33], CH 2 ( 3 B 1 and 1 A 1 ) [34], CH 3 Cl [35], HCO [36], HCN [37], and O 3 [38].…”

Section: Thermochemistrymentioning

confidence: 99%

Quantum monte carlo study of heats of formation and bond dissociation energies of small hydrocarbons

Kollias

Domin

Hill

et al. 2005

Int J of Chemical Kinetics

View full text Add to dashboard Cite

A quantum Monte Carlo (QMC) benchmark study of heats of formation at 298 K and bond dissociation energies (BDEs) of 22 small hydrocarbons is reported. Diffusion Monte Carlo (DMC) results, obtained using a simple product trial wavefunctions consisting of a single determinant and correlation function, are compared to experiment and to other theory including a version of complete basis set theory (CBS-Q) and density functional theory (DFT) with the B3LYP functional. For heats of formation, the findings are a mean absolute deviation from

show abstract

A study of vibrational anharmonicity, fermi resonance interactions, and local mode behavior in CH3Cl

Cited by 68 publications

References 47 publications

Trajectory Studies of S_N2 Nucleophilic Substitution. 7. F^- + CH₃Cl → FCH₃ + Cl^-

Trajectory Studies of S_N2 Nucleophilic Substitution. 7. F^- + CH₃Cl → FCH₃ + Cl^-

Accurate ab initio vibrational energies of methyl chloride

Quantum monte carlo study of heats of formation and bond dissociation energies of small hydrocarbons

Contact Info

Product

Resources

About

A study of vibrational anharmonicity, fermi resonance interactions, and local mode behavior in CH3Cl

Cited by 68 publications

References 47 publications

Trajectory Studies of SN2 Nucleophilic Substitution. 7. F- + CH3Cl → FCH3 + Cl-

Trajectory Studies of SN2 Nucleophilic Substitution. 7. F- + CH3Cl → FCH3 + Cl-

Accurate ab initio vibrational energies of methyl chloride

Quantum monte carlo study of heats of formation and bond dissociation energies of small hydrocarbons

Contact Info

Product

Resources

About

Trajectory Studies of S_N2 Nucleophilic Substitution. 7. F^- + CH₃Cl → FCH₃ + Cl^-

Trajectory Studies of S_N2 Nucleophilic Substitution. 7. F^- + CH₃Cl → FCH₃ + Cl^-