期刊
THEORETICAL CHEMISTRY ACCOUNTS
卷 133, 期 3, 页码 -出版社
SPRINGER
DOI: 10.1007/s00214-014-1449-x
关键词
Many-body expansion; Optical rotation; Solvation; Response properties
资金
- US National Science Foundation [CHE-1058420]
- Multi-User Chemistry Research Instrumentation and Facility (CRIF:MU) award [CHE-0741927]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1058420] Funding Source: National Science Foundation
Properties of four chiral compounds-(S)-methyloxirane, (S)-methylthiirane, (S)-2-chloropropionitrile, and (M)-dimethylallene-centered in a solvation shell of six to seven water molecules have been computed using time-dependent density functional theory at several wavelengths using a many-body expansion. Interaction energies, total system dipole moments, and dynamic dipole polarizabilities converge rapidly and smoothly, exhibiting only minor oscillations with higher-body contributions. At three-body truncation of the expansion, errors in such properties as compared to the full cluster typically fall to less than 1 % (and much smaller in most cases). Specific optical rotations, however, are found to converge much more slowly and erratically, requiring five-body contributions to obtain errors less than 5 % in three of four test cases, and six-body terms for (S)-methylthiirane. The source of this behavior is found to be the wide variation of both magnitude and sign of the specific rotation with changes in the configuration of individual solute/solvent clusters. Thus, unlike simpler properties such as energies or dipole moments, where each fragment makes a small, same-sign contribution to the total property, specific rotations typically involve much larger contributions that partly cancel in the many-body expansion. Thus, the computational costs of molecular dynamics simulations of explicit solvation, for example, will be only partially alleviated by such expansions.
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