Assessment of the SCAN Functional for Spin-State Energies in Spin-Crossover Systems

被引：23

作者：

Cirera, Jordi ^{[1
,2
]}

Ruiz, Eliseo ^{[1
,2
]}

机构：

[1] Univ Barcelona, Dept Quim Inorgan & Organ, Barcelona 08028, Spain

[2] Univ Barcelona, Inst Recerca Quim Teor & Computac, Barcelona 08028, Spain

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2020年 / 124卷 / 24期

关键词：

X-RAY-STRUCTURE; MAGNETIC-PROPERTIES; CRYSTAL-STRUCTURES; TRANSITION; COMPLEXES; TEMPERATURES; DISPERSION; BEHAVIOR;

D O I：

10.1021/acs.jpca.0c03758

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 strongly constrained and appropriately normed (SCAN) functional has been tested toward the calculation of spin-state energy differences in a data set of 20 spin-crossover (SCO) systems, ranging from d(4) to d(7). Results show that the SCAN functional is able to correctly predict the low-spin state as the ground state for all systems, and the energy window provided by the calculations falls in the approximate range of energies that will allow for SCO to occur. Moreover, the SCAN functional can be used in periodic boundary condition calculations, accounting for the effect of collective crystal vibrations and counterions in the thermochemistry of the spin transition. Our results validate this functional as a potential method for in silico screening of new SCO systems at both, molecular and crystal-packed levels.

引用

收藏

页码：5053 / 5058

页数：6

相关论文

共 50 条

[1] ELECTRONIC-STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS - THE PROGRAM SYSTEM TURBOMOLE [J].

AHLRICHS, R ;

BAR, M ;

HASER, M ;

HORN, H ;

KOLMEL, C .

CHEMICAL PHYSICS LETTERS, 1989, 162 (03) :165-169

[2] Estimation of the vibrational contribution to the entropy change associated with the low- to high-spin transition in Fe(phen)2(NCS)2 complexes:: Results obtained by IR and Raman spectroscopy and DFT calculations [J].

Brehm, G ;

Reiher, M ;

Schneider, S .

JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (50) :12024-12034

[3] Spin crossover transition of Fe(phen)2(NCS)2: periodic dispersion-corrected density-functional study [J].

Bucko, Tomas ;

Hafner, Juergen ;

Lebegue, Sebastien ;

Angyan, Janos G. .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2012, 14 (16) :5389-5396

[4] Anion doping as a probe of cooperativity in the molecular spin-crossover compound [FeL2][BF4]2 (L=2,6-di{pyrazol-1-yl}pyridine) [J].

Carbonera, Chiara ;

Kilner, Colin. A. ;

Letard, Jean-Francois ;

Halcrow, Malcolm A. .

DALTON TRANSACTIONS, 2007, (13) :1284-1292

[5] Computational Modeling of Transition Temperatures in Spin-Crossover Systems [J].

Cirera, Jordi ;

Ruiz, Eliseo .

COMMENTS ON INORGANIC CHEMISTRY, 2019, 39 (04) :216-241

[6] Benchmarking Density Functional Methods for Calculation of State Energies of First Row Spin-Crossover Molecules [J].

Cirera, Jordi ;

Via-Nadal, Mireia ;

Ruiz, Eliseo .

INORGANIC CHEMISTRY, 2018, 57 (22) :14097-14105

[7] Electronic and Steric Control of the Spin-Crossover Behavior in [(CpR)2Mn] Manganocenes [J].

Cirera, Jordi ;

Ruiz, Eliseo .

INORGANIC CHEMISTRY, 2018, 57 (02) :702-709

[8] Theoretical Modeling of the Ligand-Tuning Effect over the Transition Temperature in Four-Coordinated FeII Molecules [J].

Cirera, Jordi ;

Ruiz, Eliseo .

INORGANIC CHEMISTRY, 2016, 55 (04) :1657-1663

[9] Theoretical modeling of two-step spin-crossover transitions in FeII dinuclear systems [J].

Cirera, Jordi ;

Ruiz, Eliseo .

JOURNAL OF MATERIALS CHEMISTRY C, 2015, 3 (30) :7954-7961

[10] Theoretical Prediction of Spin-Crossover Temperatures in Ligand-Driven Light-Induced Spin Change Systems [J].

Cirera, Jordi ;

Paesani, Francesco .

INORGANIC CHEMISTRY, 2012, 51 (15) :8194-8201

← 1 2 3 4 5 →