Surprising Quenching of the Spin-Orbit Interaction Significantly Diminishes H2O•••X [X = F, Cl, Br, I] Dissociation Energies

被引：8

作者：

Czako, Gabor ^{[1
]}

Csaszar, Attila G. ^{[1
,2
]}

Schaefer, Henry F., III ^{[3
]}

机构：

[1] Eotvos Lorand Univ, Inst Chem, Lab Mol Struct & Dynam, H-1518 Budapest 12, Hungary

[2] MTA ELTE Res Grp Complex Chem Syst, H-1117 Budapest, Hungary

[3] Univ Georgia, Ctr Computat Quantum Chem, Athens, GA 30602 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2014年 / 118卷 / 51期

关键词：

BASIS-SETS; DYNAMICS; SURFACE; COMPLEX; F+H2O; ATOM;

D O I：

10.1021/jp506287z

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The H2O center dot center dot center dot X complexes, with X = F, Cl, Br, and I, show considerable viability with nonspin-orbit D-e(D-0) dissociation energy values of 3.73(2.42), 3.60(2.68), 3.54(2.72), and 3.36(2.77) kcal mol(-1) for X = F, Cl, Br, and I, respectively, obtained at the CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory using relativistic pseudopotentials (PPs) for Br and I. Spin-orbit (SO) corrections, computed with the Breit-Pauli operator in the interacting states approach at the all-electron MRCI+Q/aug-cc-pwCVTZ(-PP) level, are found to depend sensitively and unpredictably on the O center dot center dot center dot X separations. 96% (F), 87% (Cl), 54% (Br), and 30% (I) quenching of the SO corrections significantly reduces the dissociation energies of the H2O center dot center dot center dot X complexes, resulting in D-e(D-0) values of 3.38(2.06), 2.86(1.94), 1.64(0.83), and 1.23(0.64) kcal mol(-1) for X = F, Cl, Br, and I, respectively.

引用

页码：11956 / 11961

页数：6

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