The Journal of Chemical Physics最新文献_第4页

ABLRI: A program for calculating the long-range interaction energy between two monomers in their non-degenerate states ABLRI：计算两个单体在非退化状态下长程相互作用能的程序

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0205486

Yipeng Yu, Dongzheng Yang, Xixi Hu, Daiqian Xie

{"title":"ABLRI: A program for calculating the long-range interaction energy between two monomers in their non-degenerate states","authors":"Yipeng Yu, Dongzheng Yang, Xixi Hu, Daiqian Xie","doi":"10.1063/5.0205486","DOIUrl":"https://doi.org/10.1063/5.0205486","url":null,"abstract":"An accurate description of the long-range (LR) interaction is essential for understanding the collision between cold or ultracold molecules. However, to our best knowledge, there lacks a general approach to construct the intermolecular potential energy surface (IPES) between two arbitrary molecules and/or atoms in the LR region. In this work, we derived analytical expressions of the LR interaction energy, using the multipole expansion of the electrostatic interaction Hamiltonian and the non-degenerate perturbation theory. To make these formulae practical, we also derived the independent Cartesian components of the electrostatic properties, including the multipole moments and polarizabilities, of the monomer for a given symmetry using the properties of these components and the group-theoretical methods. Based on these newly derived formulae, we developed a FORTRAN program, namely ABLRI, which is capable of calculating the interaction energy between two arbitrary monomers both in their non-degenerate electronic ground states at large separations. To test the reliability of this newly developed program, we constructed IPESs for the electronic ground state of H2O–H2 and O2–H systems in the LR region. The interaction energy computed by our program agreed well with the ab initio calculation, which shows the validity of this program.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"90 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140827905","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: 0

Rate theory of gas–liquid nucleation: Quest for the elusive quantitative accuracy 气液成核的速率理论：追求难以捉摸的定量准确性

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0202884

Subhajit Acharya, Biman Bagchi

{"title":"Rate theory of gas–liquid nucleation: Quest for the elusive quantitative accuracy","authors":"Subhajit Acharya, Biman Bagchi","doi":"10.1063/5.0202884","DOIUrl":"https://doi.org/10.1063/5.0202884","url":null,"abstract":"The task of a first principles theoretical calculation of the rate of gas–liquid nucleation has remained largely incomplete despite the existence of reliable results from unbiased simulation studies at large supersaturation. Although the classical nucleation theory formulated by Becker–Doring–Zeldovich about a century ago provides an elegant, widely used picture of nucleation in a first-order phase transition, the theory finds difficulties in predicting the rate accurately, especially in the case of gas-to-liquid nucleation. Here, we use a multiple-order parameter description to construct the nucleation free energy surface needed to calculate the nucleation rate. A multidimensional non-Markovian (MDNM) rate theory formulation that generalizes Langer’s well-known nucleation theory by using the Grote–Hynes MDNM treatment is used to obtain the rate of barrier crossing. We find good agreement of the theory with the rate obtained by direct unbiased molecular dynamics simulations—the latter is feasible at large supersaturation, S. The theory gives an experimentally strong dependence of the rate of nucleation on supersaturation, S. Interestingly, we find a strong influence of the frequency-dependent friction coefficient at the barrier top. This arises from multiple recrossings of the barrier surface. We find that a Markovian theory, such as Langer’s formulation, fails to capture the rate quantitatively. In addition, the multidimensional transition state theory expression performs poorly, revealing the underlying role of the friction coefficient.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"118 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140837368","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: 0

Thermodynamics of the gas-phase dimerization of formic acid: Fully anharmonic finite temperature calculations at the CCSD(T) and many DFT levels 甲酸气相二聚化的热力学：在 CCSD(T) 和许多 DFT 水平上进行的全非谐波有限温度计算

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0205448

Dávid Vrška, Michal Pitoňák, Tomáš Bučko

{"title":"Thermodynamics of the gas-phase dimerization of formic acid: Fully anharmonic finite temperature calculations at the CCSD(T) and many DFT levels","authors":"Dávid Vrška, Michal Pitoňák, Tomáš Bučko","doi":"10.1063/5.0205448","DOIUrl":"https://doi.org/10.1063/5.0205448","url":null,"abstract":"A proof-of-concept study is undertaken to demonstrate the utility of the machine learning combined with the thermodynamic perturbation theory (MLPT) to test the accuracy of electronic structure methods in finite-temperature thermodynamic calculations. As a test example, formic acid dimer is chosen, which is one of the systems included in the popular benchmark set S22 [Jurečka et al., Phys. Chem. Chem. Phys. 8, 1985–1993 (2006)]. Starting from the explicit molecular dynamics and thermodynamic integration performed at the PBE + D2 level, the MLPT is used to obtain fully anharmonic dimerization free and internal energies at the reference quality CCSD(T) level and 19 different density functional approximations, including GGA, meta-GGA, non-local, and hybrid functionals with and without dispersion corrections. Our finite-temperature results are shown to be both qualitatively and quantitatively different from those obtained using the conventional benchmarking strategy based on fixed structures. The hybrid functional HSE06 is identified as the best performing approximate method tested, with the errors in free and internal energies of dimerization being 36 and 41 meV, respectively.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"107 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140827653","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: 0

Switch the click: Ultrafast photochemistry of photoDIBO-OH tracked by time-resolved IR spectroscopy 切换点击通过时间分辨红外光谱追踪光二溴乙烷-OH 的超快光化学过程

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0196923

L. Denninger, H. Brunst, L. J. G. W. van Wilderen, M. Horz, H. M. A. Masood, C. D. McNitt, I. Burghardt, V. V. Popik, J. Bredenbeck

引用次数: 0

Energy decomposition analysis method using density matrix formulation 使用密度矩阵公式的能量分解分析方法

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0202787

Yueyang Zhang, Longxiang Yan, Wei Wu, Peifeng Su

引用次数: 0

Prediction through quantum dynamics simulations: Photo-excited cyclobutanone 通过量子动力学模拟进行预测：光激发环丁酮

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0203654

Olivia Bennett, Antonia Freibert, K. Eryn Spinlove, Graham A. Worth

{"title":"Prediction through quantum dynamics simulations: Photo-excited cyclobutanone","authors":"Olivia Bennett, Antonia Freibert, K. Eryn Spinlove, Graham A. Worth","doi":"10.1063/5.0203654","DOIUrl":"https://doi.org/10.1063/5.0203654","url":null,"abstract":"Quantum dynamics simulations are becoming a standard tool for simulating photo-excited molecular systems involving a manifold of coupled states, known as non-adiabatic dynamics. While these simulations have had many successes in explaining experiments and giving details of non-adiabatic transitions, the question remains as to their predictive power. In this work, we present a set of quantum dynamics simulations on cyclobutanone using both grid-based multi-configuration time-dependent Hartree and direct dynamics variational multi-configuration Gaussian methods. The former used a parameterized vibronic coupling model Hamiltonian, and the latter generated the potential energy surfaces on the fly. The results give a picture of the non-adiabatic behavior of this molecule and were used to calculate the signal from a gas-phase ultrafast electron diffraction (GUED) experiment. Corresponding experimental results will be obtained and presented at a later stage for comparison to test the predictive power of the methods. The results show that over the first 500 fs after photo-excitation to the S2 state, cyclobutanone relaxes quickly to the S1 state, but only a small population relaxes further to the S0 state. No significant transfer of population to the triplet manifold is found. It is predicted that the GUED experiments over this time scale will see signals related mostly to the C–O stretch motion and elongation of the molecular ring along the C–C–O axis.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140837507","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: 0

Simple and efficient methods for local structural analysis in polydisperse hard disk systems 用于多分散硬盘系统局部结构分析的简单高效方法

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0194873

Daigo Mugita, Kazuyoshi Souno, Hiroaki Koyama, Taisei Nakamura, Masaharu Isobe

引用次数: 0

Seamless integration of GEM, a density based-force field, for QM/MM simulations via LICHEM, Psi4, and Tinker-HP 通过 LICHEM、Psi4 和 Tinker-HP 将基于密度的力场 GEM 无缝集成到 QM/MM 模拟中

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0200722

Jorge Nochebuena, Andrew C. Simmonett, G. Andrés Cisneros

{"title":"Seamless integration of GEM, a density based-force field, for QM/MM simulations via LICHEM, Psi4, and Tinker-HP","authors":"Jorge Nochebuena, Andrew C. Simmonett, G. Andrés Cisneros","doi":"10.1063/5.0200722","DOIUrl":"https://doi.org/10.1063/5.0200722","url":null,"abstract":"Hybrid quantum mechanics/molecular mechanics (QM/MM) simulations have become an essential tool in computational chemistry, particularly for analyzing complex biological and condensed phase systems. Building on this foundation, our work presents a novel implementation of the Gaussian Electrostatic Model (GEM), a polarizable density-based force field, within the QM/MM framework. This advancement provides seamless integration, enabling efficient and optimized QM/GEM calculations in a single step using the LICHEM Code. We have successfully applied our implementation to water dimers and hexamers, demonstrating the ability to handle water systems with varying numbers of water molecules. Moreover, we have extended the application to describe the double proton transfer of the aspartic acid dimer in a box of water, which highlights the method’s proficiency in investigating heterogeneous systems. Our implementation offers the flexibility to perform on-the-fly density fitting or to utilize pre-fitted coefficients to estimate exchange and Coulomb contributions. This flexibility enhances efficiency and accuracy in modeling molecular interactions, especially in systems where polarization effects are significant.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140837200","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: 0

Insights into thiocyanate-enhanced photoluminescence in CsPbBr3 nanocrystals by ultrafast two-dimensional infrared spectroscopy 通过超快二维红外光谱深入了解硫氰酸盐增强的 CsPbBr3 纳米晶体中的光致发光

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0200873

Arghyadeep Basu, Nathan Rafisiman, Saar Shaek, Rachel Lifer, Vivek Yadav, Yaron Kauffmann, Yehonadav Bekenstein, Lev Chuntonov

{"title":"Insights into thiocyanate-enhanced photoluminescence in CsPbBr3 nanocrystals by ultrafast two-dimensional infrared spectroscopy","authors":"Arghyadeep Basu, Nathan Rafisiman, Saar Shaek, Rachel Lifer, Vivek Yadav, Yaron Kauffmann, Yehonadav Bekenstein, Lev Chuntonov","doi":"10.1063/5.0200873","DOIUrl":"https://doi.org/10.1063/5.0200873","url":null,"abstract":"Functionalization of perovskite nanocrystal surfaces with thiocyanate anions presents a transformative approach to enhancing stability and photoluminescence quantum yield (PLQY) through surface defect passivation. This study investigates the role of thiocyanate ligands in modifying the optoelectronic properties of CsPbBr3 nanocrystals. We employed ultrafast two-dimensional infrared spectroscopy to investigate the nature of the dynamic interaction of thiocyanate ligands with nanocrystal surfaces, providing insights into the mechanisms underlying the observed increase in PLQY and stability. Our analysis reveals that the thiocyanate ligands efficiently passivate the surface defects, thereby enhancing the PLQY and the stability of the treated nanocrystals. The spectroscopic evidence supports a model where thiocyanate binds to under-coordinated lead atoms, contributing to a stable nanocrystal surface with enhanced optoelectronic performance. This ligand-induced passivation mechanism advances our understanding of surface chemistry's role in optimizing nanomaterials for solar cell and LED applications.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"54 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140827654","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: 0

Exploring electron donor and acceptor effects: DFT analysis of ESIPT/GSIPT in 2-(oxazolinyl)-phenols for photophysical and luminophore enhancement 探索电子供体和受体效应：DFT 分析 2-（噁唑啉基）-苯酚中的 ESIPT/GSIPT 对光物理和发光体的增强作用

The Journal of Chemical Physics Pub Date : 2024-05-01 DOI: 10.1063/5.0202890

Murugesan Panneerselvam, Reshma Rensil Francis, Singaravel Nathiya, Rajadurai Vijay Solomon, Madhavan Jaccob, Luciano T. Costa

{"title":"Exploring electron donor and acceptor effects: DFT analysis of ESIPT/GSIPT in 2-(oxazolinyl)-phenols for photophysical and luminophore enhancement","authors":"Murugesan Panneerselvam, Reshma Rensil Francis, Singaravel Nathiya, Rajadurai Vijay Solomon, Madhavan Jaccob, Luciano T. Costa","doi":"10.1063/5.0202890","DOIUrl":"https://doi.org/10.1063/5.0202890","url":null,"abstract":"Understanding excited-state intramolecular proton transfer (ESIPT) is essential for designing organic molecules to enhance photophysical and luminophore properties in the development of optoelectronic devices. In this context, an attempt has been made to understand the impact of substituents on the ESIPT process of 2-(oxazolinyl)-phenol. Electron donating (EDG: –NH2, –OCH3, and –CH3) and electron withdrawing (EWG: –Cl, –Br, –COOH, –CF3, –CN, and –NO2) substitutions have been computationally designed and screened through density functional theory (DFT) and time-dependent density-functional theory (TDDFT) calculations. Furthermore, the ground state intramolecular proton transfer and ESIPT mechanisms of these designed luminophores are explored using the transition state theory. The results reveal that molecules with EDG show higher absorption and emission peaks than molecules with EWG and also indicate that the mobility of charge carriers in 2-(oxazolinyl)-phenol derivatives is significantly influenced by substituents. We found that the EWGs decrease the reorganization energy and increase the vertical ionization potential and electron affinity values, as well as the highest occupied molecular orbital-lowest unoccupied molecular orbital gap, compared to the EDG substituted molecules. Significantly, the excited state (S1) of the keto emission (K) form shows notably larger values for the EDG substitutions. The intersystem crossing pathway efficiency weakens with reduced spin–orbit coupling matrix element in the enol form with electron-donating substituents and vice versa in the keto form during S1–T3 transitions. Our research links intramolecular proton transfers and triplet generation, making these substituted molecules appealing for optoelectronic devices. Introducing EDGs, such as –NH2, boosts the ESIPT reaction in 2-(oxazolinyl)-phenol. This study guides designing ESIPT emitters with unique photophysical properties.","PeriodicalId":501648,"journal":{"name":"The Journal of Chemical Physics","volume":"17 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140827558","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: 0