MP2 studies of relativistic effects on the linear stationary points of the H + Cl2 → HCl + Cl and Cl + HCl → ClH + Cl reactions

L. Visscher; K.G. Dyall

doi:10.1016/0009-2614(95)00435-7

MP2 studies of relativistic effects on the linear stationary points of the H + Cl2 → HCl + Cl and Cl + HCl → ClH + Cl reactions

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Abstract

The influence of relativistic effects on the linear stationary points of the potential energy surfaces of the ClHCl and HCl2 systems is studied. Scalar relativistic effects have little influence on the geometries and the energies at these points. Spin-orbit effects have no influence on the barrier of the forward reaction of H with Cl2, but increase the reaction energy. The total relativistic effect is an increase of the reaction energy by 2.3 kJ mol−1. The barrier for the iso-energetic exchange reaction of HCl with Cl is decreased by 0.5 kJ mol−1 due to the scalar relativistic effects. This small decrease is cancelled by the larger increase of 2.5 kJ mol−1 due to spin-orbit effects, giving a total relativistic effect of 2.0 kJ mol−1.

Original language	English
Pages (from-to)	181-185
Number of pages	5
Journal	Chemical Physics Letters
Volume	239
Issue number	1-3
DOIs	https://doi.org/10.1016/0009-2614(95)00435-7
Publication status	Published - 9 Jun 1995
Externally published	Yes

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@article{ba965781551d47c68437cd9ebe1003fb,

title = "MP2 studies of relativistic effects on the linear stationary points of the H + Cl2 → HCl + Cl and Cl + HCl → ClH + Cl reactions",

abstract = "The influence of relativistic effects on the linear stationary points of the potential energy surfaces of the ClHCl and HCl2 systems is studied. Scalar relativistic effects have little influence on the geometries and the energies at these points. Spin-orbit effects have no influence on the barrier of the forward reaction of H with Cl2, but increase the reaction energy. The total relativistic effect is an increase of the reaction energy by 2.3 kJ mol−1. The barrier for the iso-energetic exchange reaction of HCl with Cl is decreased by 0.5 kJ mol−1 due to the scalar relativistic effects. This small decrease is cancelled by the larger increase of 2.5 kJ mol−1 due to spin-orbit effects, giving a total relativistic effect of 2.0 kJ mol−1.",

author = "L. Visscher and K.G. Dyall",

year = "1995",

month = jun,

day = "9",

doi = "10.1016/0009-2614(95)00435-7",

language = "English",

volume = "239",

pages = "181--185",

journal = "Chemical Physics Letters",

issn = "0009-2614",

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number = "1-3",

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TY - JOUR

T1 - MP2 studies of relativistic effects on the linear stationary points of the H + Cl2 → HCl + Cl and Cl + HCl → ClH + Cl reactions

AU - Visscher, L.

AU - Dyall, K.G.

PY - 1995/6/9

Y1 - 1995/6/9

N2 - The influence of relativistic effects on the linear stationary points of the potential energy surfaces of the ClHCl and HCl2 systems is studied. Scalar relativistic effects have little influence on the geometries and the energies at these points. Spin-orbit effects have no influence on the barrier of the forward reaction of H with Cl2, but increase the reaction energy. The total relativistic effect is an increase of the reaction energy by 2.3 kJ mol−1. The barrier for the iso-energetic exchange reaction of HCl with Cl is decreased by 0.5 kJ mol−1 due to the scalar relativistic effects. This small decrease is cancelled by the larger increase of 2.5 kJ mol−1 due to spin-orbit effects, giving a total relativistic effect of 2.0 kJ mol−1.

AB - The influence of relativistic effects on the linear stationary points of the potential energy surfaces of the ClHCl and HCl2 systems is studied. Scalar relativistic effects have little influence on the geometries and the energies at these points. Spin-orbit effects have no influence on the barrier of the forward reaction of H with Cl2, but increase the reaction energy. The total relativistic effect is an increase of the reaction energy by 2.3 kJ mol−1. The barrier for the iso-energetic exchange reaction of HCl with Cl is decreased by 0.5 kJ mol−1 due to the scalar relativistic effects. This small decrease is cancelled by the larger increase of 2.5 kJ mol−1 due to spin-orbit effects, giving a total relativistic effect of 2.0 kJ mol−1.

U2 - 10.1016/0009-2614(95)00435-7

DO - 10.1016/0009-2614(95)00435-7

M3 - Article

SN - 0009-2614

VL - 239

SP - 181

EP - 185

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-3

ER -

MP2 studies of relativistic effects on the linear stationary points of the H + Cl2 → HCl + Cl and Cl + HCl → ClH + Cl reactions

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