The performance of density function theory in describing gas-phase SN2 reactions at saturated nitrogen

Yi Ren; Joel L. Wolk; Shmaryahu Hoz

doi:10.1016/s1387-3806(02)00894-1

The performance of density function theory in describing gas-phase S_N2 reactions at saturated nitrogen

Yi Ren, Joel L. Wolk, Shmaryahu Hoz

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

The prototype gas-phase identity S_N2 reactions at neutral nitrogen X^- + NH₂X → NH₂X + X^- (where X = F, Cl, Br, I) were studied using the three hybrid Hartree-Fock DFT methods B3LYP, MPW1PW and MPW1K in conjunction with the 6-31+G(d,p) basis sets. Comparison of the results with the high-level G2(+) theory indicated that all of the three hybrid DFT methods can give reasonable values of the complexation energies (ΔH_comp) for the ion-molecule complex formed in the reaction X^- + NH₂X (X = Cl, Br, I). The overall barriers (ΔH_ovr^≠) and central barriers (ΔH_cent^≠) for all of the reactions calculated using B3LYP functional are significantly underestimated. The best transition structures were obtained using MPW1K/6-31+G(d,p) level, which appears to exhibit the best performance in describing the potential energy surface for S_N2 reactions at neutral nitrogen. Some correlations of central barriers found at the G2(+) level of theory are reproduced by the results of three hybrid DFT methods for the reactions X^- + NH₂X → NH₂X + X^- (X = Cl, Br, I).

Original language	English
Pages (from-to)	59-65
Number of pages	7
Journal	International Journal of Mass Spectrometry
Volume	221
Issue number	1
DOIs	https://doi.org/10.1016/s1387-3806(02)00894-1
State	Published - 1 Nov 2002

Bibliographical note

Funding Information:
This work was supported by the Barbara and Kort Sino-Israel Post-Doctoral Fellowship Program, the Scientific Research Foundation for the Returned Chinese Scholars of State Education Ministry and Scientific Research Foundation for the Young Teacher of Sichuan University.

Funding

This work was supported by the Barbara and Kort Sino-Israel Post-Doctoral Fellowship Program, the Scientific Research Foundation for the Returned Chinese Scholars of State Education Ministry and Scientific Research Foundation for the Young Teacher of Sichuan University.

Funders	Funder number
Barbara and Kort Sino-Israel
Scientific Research Foundation for the Returned Chinese Scholars of State Education Ministry and Scientific Research Foundation for the Young Teacher of Sichuan University

Keywords

Complexation energies
Nucleophilic substitution reaction
Transition state

Access to Document

10.1016/s1387-3806(02)00894-1

Cite this

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title = "The performance of density function theory in describing gas-phase SN2 reactions at saturated nitrogen",

abstract = "The prototype gas-phase identity SN2 reactions at neutral nitrogen X- + NH2X → NH2X + X- (where X = F, Cl, Br, I) were studied using the three hybrid Hartree-Fock DFT methods B3LYP, MPW1PW and MPW1K in conjunction with the 6-31+G(d,p) basis sets. Comparison of the results with the high-level G2(+) theory indicated that all of the three hybrid DFT methods can give reasonable values of the complexation energies (ΔHcomp) for the ion-molecule complex formed in the reaction X- + NH2X (X = Cl, Br, I). The overall barriers (ΔHovr≠) and central barriers (ΔHcent≠) for all of the reactions calculated using B3LYP functional are significantly underestimated. The best transition structures were obtained using MPW1K/6-31+G(d,p) level, which appears to exhibit the best performance in describing the potential energy surface for SN2 reactions at neutral nitrogen. Some correlations of central barriers found at the G2(+) level of theory are reproduced by the results of three hybrid DFT methods for the reactions X- + NH2X → NH2X + X- (X = Cl, Br, I).",

keywords = "Complexation energies, Nucleophilic substitution reaction, Transition state",

author = "Yi Ren and Wolk, {Joel L.} and Shmaryahu Hoz",

note = "Funding Information: This work was supported by the Barbara and Kort Sino-Israel Post-Doctoral Fellowship Program, the Scientific Research Foundation for the Returned Chinese Scholars of State Education Ministry and Scientific Research Foundation for the Young Teacher of Sichuan University.",

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AU - Wolk, Joel L.

AU - Hoz, Shmaryahu

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N2 - The prototype gas-phase identity SN2 reactions at neutral nitrogen X- + NH2X → NH2X + X- (where X = F, Cl, Br, I) were studied using the three hybrid Hartree-Fock DFT methods B3LYP, MPW1PW and MPW1K in conjunction with the 6-31+G(d,p) basis sets. Comparison of the results with the high-level G2(+) theory indicated that all of the three hybrid DFT methods can give reasonable values of the complexation energies (ΔHcomp) for the ion-molecule complex formed in the reaction X- + NH2X (X = Cl, Br, I). The overall barriers (ΔHovr≠) and central barriers (ΔHcent≠) for all of the reactions calculated using B3LYP functional are significantly underestimated. The best transition structures were obtained using MPW1K/6-31+G(d,p) level, which appears to exhibit the best performance in describing the potential energy surface for SN2 reactions at neutral nitrogen. Some correlations of central barriers found at the G2(+) level of theory are reproduced by the results of three hybrid DFT methods for the reactions X- + NH2X → NH2X + X- (X = Cl, Br, I).

AB - The prototype gas-phase identity SN2 reactions at neutral nitrogen X- + NH2X → NH2X + X- (where X = F, Cl, Br, I) were studied using the three hybrid Hartree-Fock DFT methods B3LYP, MPW1PW and MPW1K in conjunction with the 6-31+G(d,p) basis sets. Comparison of the results with the high-level G2(+) theory indicated that all of the three hybrid DFT methods can give reasonable values of the complexation energies (ΔHcomp) for the ion-molecule complex formed in the reaction X- + NH2X (X = Cl, Br, I). The overall barriers (ΔHovr≠) and central barriers (ΔHcent≠) for all of the reactions calculated using B3LYP functional are significantly underestimated. The best transition structures were obtained using MPW1K/6-31+G(d,p) level, which appears to exhibit the best performance in describing the potential energy surface for SN2 reactions at neutral nitrogen. Some correlations of central barriers found at the G2(+) level of theory are reproduced by the results of three hybrid DFT methods for the reactions X- + NH2X → NH2X + X- (X = Cl, Br, I).

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