Practical electronic ground-and excited-state calculation method for lanthanide complexes based on frozen core potential approximation to 4f electrons

被引：1

作者：

Kobayashi, Masato ^{[1
,2
,3
]}

Oba, Yuta ^{[4
]}

Akama, Tomoko ^{[1
]}

Taketsugu, Tetsuya ^{[1
,2
,3
]}

机构：

[1] Hokkaido Univ, Fac Sci, Dept Chem, Sapporo, Hokkaido 0600810, Japan

[2] Hokkaido Univ, WPI ICReDD, Sapporo, Hokkaido 0010021, Japan

[3] Kyoto Univ, ESICB, Kyoto 6158520, Japan

[4] Hokkaido Univ, Grad Sch Chem Sci & Engn, Sapporo, Hokkaido 0600810, Japan

来源：

JOURNAL OF MATHEMATICAL CHEMISTRY | 2023年 / 61卷 / 02期

关键词：

Frozen 4f core potential approximation; Lanthanide complexes; Elongation method; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; AB-INITIO; ELONGATION METHOD; POLYMERS; ATOMS; LOCALIZATION; ORBITALS;

D O I：

10.1007/s10910-022-01356-5

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A practical electronic ground- and excited-state calculation method for lanthanide complexes is proposed by introducing frozen core potential (FCP) approximation to 4f electrons of a lanthanide atom ion (Ln(3+)). Based on the fact that the FCP method is formally equivalent to the elongation method, the 4f-frozen FCP calculations of Ln(3+) complexes were successfully performed using the elongation method implemented in GAMESS quantum chemistry program. By comparing the 4f-frozen FCP calculation results of several lanthanide complexes with the results of the standard calculations, it was confirmed that the excitation energies by these calculations are comparable. Also, the SCF convergence and stability were significantly improved by the FCP approximation. We further propose a method to relax the rotational degrees of freedom for the frozen 4f orbitals. This relaxation slightly improves the accuracy of the excitation energies for f-f transitions.

引用

页码：322 / 334

页数：13