Environment Effects on X-Ray Absorption Spectra With Quantum Embedded Real-Time Time-Dependent Density Functional Theory Approaches

被引:4
作者
De Santis, Matteo [1 ]
Vallet, Valerie [1 ]
Gomes, Andre Severo Pereira [1 ]
机构
[1] Univ Lille, UMR 8523 PhLAM Phys Lasers Atomes & Mol, CNRS, Lille, France
关键词
real-time propagation; time-dependent density functional theory; frozen density embedding; block-orthogonalized manby-miller embedding; X-ray absorption spectroscopy; halides; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; ELECTRON DYNAMICS; SOFTWARE NEWS; DECOMPOSITION; SPECTROSCOPY; EXCITATIONS; CHEMISTRY; FIELD;
D O I
10.3389/fchem.2022.823246
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this work we implement the real-time time-dependent block-orthogonalized Manby-Miller embedding (rt-BOMME) approach alongside our previously developed real-time frozen density embedding time-dependent density functional theory (rt-TDDFT-in-DFT FDE) code, and investigate these methods' performance in reproducing X-ray absorption spectra (XAS) obtained with standard rt-TDDFT simulations, for model systems comprised of solvated fluoride and chloride ions ([X@ ( H2O)(8)](-) , X = F, Cl). We observe that for ground-state quantities such as core orbital energies, the BOMME approach shows significantly better agreement with supermolecular results than FDE for the strongly interacting fluoride system, while for chloride the two embedding approaches show more similar results. For the excited states, we see that while FDE (constrained not to have the environment densities relaxed in the ground state) is in good agreement with the reference calculations for the region around the K and L-1 edges, and is capable of reproducing the splitting of the 1s(1) (n + 1)p(1) final states (n + 1 being the lowest virtual p orbital of the halides), it by and large fails to properly reproduce the 1s(1) (n + 2)p(1) states and misses the electronic states arising from excitation to orbitals with important contributions from the solvent. The BOMME results, on the other hand, provide a faithful qualitative representation of the spectra in all energy regions considered, though its intrinsic approximation of employing a lower-accuracy exchange-correlation functional for the environment induces non-negligible shifts in peak positions for the excitations from the halide to the environment. Our results thus confirm that QM/QM embedding approaches are viable alternatives to standard real-time simulations of X-ray absorption spectra of species in complex or confined environments.
引用
收藏
页数:14
相关论文
共 101 条
[1]   Interfacial supercooling and the precipitation of hydrohalite in frozen NaCl solutions as seen by X-ray absorption spectroscopy [J].
Bartels-Rausch, Thorsten ;
Kong, Xiangrui ;
Orlando, Fabrizio ;
Artiglia, Luca ;
Waldner, Astrid ;
Huthwelker, Thomas ;
Ammann, Markus .
CRYOSPHERE, 2021, 15 (04) :2001-2020
[2]   Modeling of the spectroscopy of core electrons with density functional theory [J].
Besley, Nicholas A. .
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE, 2021, 11 (06)
[3]   Time-dependent density functional theory calculations of the spectroscopy of core electrons [J].
Besley, Nicholas A. ;
Asmuruf, Frans A. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (38) :12024-12039
[4]   The weak covalent bond in NgAuF (Ng=Ar, Kr, Xe): A challenge for subsystem density functional theory [J].
Beyhan, S. Maya ;
Gotz, Andreas W. ;
Jacob, Christoph R. ;
Visscher, Lucas .
JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (04)
[5]  
Bouchafra Y., 2018, Predictive Simulations of Ionization Energies of Solvated Halide Ions with Relativistic Embedded Equation of Motion Coupled-Cluster Theory, DOI 10.5281/zenodo.1477004
[6]   Predictive Simulations of Ionization Energies of Solvated Halide Ions with Relativistic Embedded Equation of Motion Coupled Cluster Theory [J].
Bouchafra, Yassine ;
Shee, Avijit ;
Real, Florent ;
Vallet, Valerie ;
Gomes, Andre Severo Pereira .
PHYSICAL REVIEW LETTERS, 2018, 121 (26)
[7]   Accelerated Broadband Spectra Using Transition Dipole Decomposition and Pade Approximants [J].
Bruner, Adam ;
LaMaster, Daniel ;
Lopata, Kenneth .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2016, 12 (08) :3741-3750
[8]  
Bunker G., 2010, Introduction to XAFS, DOI [10.1017/CBO9780511809194, DOI 10.1017/CBO9780511809194]
[9]   Propagators for the time-dependent Kohn-Sham equations [J].
Castro, A ;
Marques, MAL ;
Rubio, A .
JOURNAL OF CHEMICAL PHYSICS, 2004, 121 (08) :3425-3433
[10]   Simulating molecular conductance using real-time density functional theory [J].
Cheng, Chiao-Lun ;
Evans, Jeremy S. ;
Van Voorhis, Troy .
PHYSICAL REVIEW B, 2006, 74 (15)