arXiv: Chemical Physics最新文献_第10页

Interpolated Wave Functions for Nonadiabatic Simulations with the Fixed-Node Quantum Monte Carlo Method 用固定节点量子蒙特卡罗方法进行非绝热模拟的内插波函数

arXiv: Chemical Physics Pub Date : 2016-07-10 DOI: 10.1021/BK-2016-1234.CH003

N. Tubman, Yubo Yang, S. Hammes‐Schiffer, D. Ceperley

引用次数: 1

Accurate Non-adiabatic Quantum Dynamics from Pseudospectral Sampling of Time-dependent Gaussian Basis Sets 基于时变高斯基集伪谱采样的精确非绝热量子动力学

arXiv: Chemical Physics Pub Date : 2016-06-20 DOI: 10.1063/1.4959872

C. Heaps, D. Mazziotti

{"title":"Accurate Non-adiabatic Quantum Dynamics from Pseudospectral Sampling of Time-dependent Gaussian Basis Sets","authors":"C. Heaps, D. Mazziotti","doi":"10.1063/1.4959872","DOIUrl":"https://doi.org/10.1063/1.4959872","url":null,"abstract":"Quantum molecular dynamics requires an accurate representation of the molecular potential energy surface from a minimal number of electronic structure calculations, particularly for nonadiabatic dynamics where excited states are required. In this paper, we employ pseudospectral sampling of time-dependent Gaussian basis functions for the simulation of non-adiabatic dynamics. Unlike other methods, the pseudospectral Gaussian molecular dynamics tests the Schrodinger equation with $N$ Dirac delta functions located at the centers of the Gaussian functions reducing the scaling of potential energy evaluations from $mathcal{O}(N^2)$ to $mathcal{O}(N)$. By projecting the Gaussian basis onto discrete points in space, the method is capable of efficiently and quantitatively describing nonadiabatic population transfer and intra-surface quantum coherence. We investigate three model systems; the photodissociation of three coupled Morse oscillators, the bound state dynamics of two coupled Morse oscillators, and a two-dimensional model for collinear triatomic vibrational dynamics. In all cases, the pseudospectral Gaussian method is in quantitative agreement with numerically exact calculations. The results are promising for nonadiabatic molecular dynamics in molecular systems where strongly correlated ground or excited states require expensive electronic structure calculations.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76646882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 4

Electronic friction near metal surfaces: a case where molecule-metal couplings depend on nuclear coordinates 金属表面附近的电子摩擦:分子-金属耦合依赖于核坐标的一种情况

arXiv: Chemical Physics Pub Date : 2016-06-20 DOI: 10.1063/1.4965823

Wenjie Dou, Joseph E. Subotnik

引用次数: 32

On the mass of atoms in molecules: Beyond the Born-Oppenheimer approximation 论分子中原子的质量:超越玻恩-奥本海默近似

arXiv: Chemical Physics Pub Date : 2016-05-13 DOI: 10.1103/PhysRevX.7.031035

A. Scherrer, F. Agostini, D. Sebastiani, E. Gross, R. Vuilleumier

{"title":"On the mass of atoms in molecules: Beyond the Born-Oppenheimer approximation","authors":"A. Scherrer, F. Agostini, D. Sebastiani, E. Gross, R. Vuilleumier","doi":"10.1103/PhysRevX.7.031035","DOIUrl":"https://doi.org/10.1103/PhysRevX.7.031035","url":null,"abstract":"Describing the dynamics of nuclei in molecules requires a potential energy surface, which is traditionally provided by the Born-Oppenheimer or adiabatic approximation. However, we also need to assign masses to the nuclei. There, the Born-Oppenheimer picture does not account for the inertia of the electrons and only bare nuclear masses are considered. Nowadays, experimental accuracy challenges the theoretical predictions of rotational and vibrational spectra and requires to include the participation of electrons in the internal motion of the molecule. More than 80 years after the original work of Born and Oppenheimer, this issue still is not solved in general. Here, we present a theoretical and numerical framework to address this problem in a general and rigorous way. Starting from the exact factorization of the electron-nuclear wave function, we include electronic effects beyond the Born-Oppenheimer regime in a perturbative way via position-dependent corrections to the bare nuclear masses. This maintains an adiabatic-like point of view: the nuclear degrees of freedom feel the presence of the electrons via a single potential energy surface, whereas the inertia of electrons is accounted for and the total mass of the system is recovered. This constitutes a general framework for describing the mass acquired by slow degrees of freedom due to the inertia of light, bounded particles. We illustrate it with a model of proton transfer, where the light particle is the proton, and with corrections to the vibrational spectra of molecules. Inclusion of the light particle inertia allows to gain orders of magnitude in accuracy.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91325339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 35

Linear-scaling generation of potential energy surfaces using a double incremental expansion 使用双增量展开的势能曲面的线性缩放生成

arXiv: Chemical Physics Pub Date : 2016-05-05 DOI: 10.1063/1.4960189

Carolin Konig, O. Christiansen

引用次数: 40

Electron Transfer Pathway Analysis in Bacterial Photosynthetic Reaction Center 细菌光合反应中心电子传递途径分析

arXiv: Chemical Physics Pub Date : 2016-04-07 DOI: 10.1007/978-4-431-55357-1_39

Hirotaka Kitoh-Nishioka, K. Ando

引用次数: 0

Solar water splitting: efficiency discussion 太阳能水分解:效率讨论

arXiv: Chemical Physics Pub Date : 2016-04-05 DOI: 10.1016/J.IJHYDENE.2016.05.079

J. Juodkazytė, G. Seniutinas, B. Šebeka, I. Savickaja, T. Malinauskas, K. Badokas, K. Juodkazis, S. Juodkazis

引用次数: 35

Localization of the valence electron of endohedrally confined hydrogen, lithium and sodium in fullerene cages 富勒烯笼中内源性限制氢、锂和钠的价电子定位

arXiv: Chemical Physics Pub Date : 2016-03-08 DOI: 10.1142/S0217979216500557

E. Cuestas, P. Serra

引用次数: 4

Electronic and Optical Properties of the Narrowest Armchair Graphene Nanoribbons Studied by Density Functional Methods 用密度泛函方法研究最窄扶手椅石墨烯纳米带的电子和光学性质

arXiv: Chemical Physics Pub Date : 2016-01-16 DOI: 10.1071/CH16187

Chia-Nan Yeh, Pei-Yin Lee, Jeng-Da Chai

引用次数: 9

Interfacial Thermal Conductance of Thiolate-Protected Gold Nanospheres 硫代酸保护金纳米球的界面热导率

arXiv: Chemical Physics Pub Date : 2016-01-13 DOI: 10.1063/1.4939956

Kelsey M. Stocker, Suzanne M. Neidhart, J. D. Gezelter

{"title":"Interfacial Thermal Conductance of Thiolate-Protected Gold Nanospheres","authors":"Kelsey M. Stocker, Suzanne M. Neidhart, J. D. Gezelter","doi":"10.1063/1.4939956","DOIUrl":"https://doi.org/10.1063/1.4939956","url":null,"abstract":"Molecular dynamics simulations of thiolate-protected and solvated gold nanoparticles were carried out in the presence of a non-equilibrium heat flux between the solvent and the core of the particle. The interfacial thermal conductance ($G$) was computed for these interfaces, and the behavior of the thermal conductance was studied as a function of particle size, ligand flexibility, and ligand chain length. In all cases, thermal conductance of the ligand-protected particles was higher than the bare metal-solvent interface. A number of mechanisms for the enhanced conductance were investigated, including thiolate-driven corrugation of the metal surface, solvent ordering at the interface, solvent-ligand interpenetration, and ligand ordering relative to the particle surface. Only the smallest particles exhibited significant corrugation. All ligands permitted substantial solvent-ligand interpenetration, and ligand chain length has a significant influence on the orientational ordering of interfacial solvent. Solvent-ligand vibrational overlap, particularly in the low frequency range ($< 80 mathrm{cm}^{-1}$) was significantly altered by ligand rigidity, and had direct influence on the interfacial thermal conductance.","PeriodicalId":8439,"journal":{"name":"arXiv: Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2016-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88800749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 27