Electronic Potential Energy Research Articles

A multimass velocity-map and covariance-map imaging study of the dissociative electron ionisation dynamics of carbonyl sulphide (OCS)

Abstract We present the results of a velocity-map imaging study into the dissociative electron ionisation dynamics of OCS at electron energies of 50, 75, and 100 eV, supported by new EOM-CCSD and CASSCF potential energy surface calculations for the OCS+ cation and OCS2+ dication. We report partial ionisation cross-sections and scattering distributions for the observed ionic fragments, and interpret these in terms of the dissociation dynamics of the singly and doubly charged OCS parent ions formed in the electron-molecule collisions. For many of the dissociation channels, consideration of the calculated potential energy surfaces supplemented by comparison with data from photoionisation studies provides insight into the electronic potential energy surfaces involved. For fragmentation products arising from dissociation of the dication, time-of-flight and recoil-frame covariance maps provide mechanistic insight into the stepwise dissociation mechanisms leading to these products and support previous conclusions by other authors.

QSLE-v1.0: A New Software Package for the Calculation of Coupled Quantum-Classical Dynamics in Condensed Phases Based on a Stochastic Approach.

Recently, a stochastic version of the quantum-classical Liouville equation has been proposed [Campeggio, J.; Cortivo, R.; Zerbetto, M. J. Chem. Phys. 2023, 158, 244104], to compute the coupled quantum-classical dynamics of molecules in condensed phases. The approach, called quantum-stochastic Liouville equation (QSLE), is based on coupling the time evolution of electronic states to a stochastic description of the relevant (classical) nuclear coordinates. Natural internal coordinates are used, i.e., bond lengths, bond angles, and dihedral angles. The approach is tailored to directly propagate the populations of the electronic states over time, based on a classical Fokker-Planck equation for the nuclear degrees of freedom coupled to a master equation for the jumps among the electronic states. The QSLE is a multiscale approach requiring many ingredients to be assembled in order to carry out the numerical solution. To make the approach accessible, a software package that handles the main (and most cumbersome) details of the numerical workflow has been implemented into the software package QSLE-v1.0, which is introduced in the present paper. Here, it is considered the case of one torsional nuclear coordinate and two nonadiabatic electronic potential energy surfaces. This is a very basic model for interpreting photoisomerization or charge transfer phenomena, but despite its simplicity, it can be applied even in complex systems where the relevant quantum/classical parts affecting the phenomena under study are highly localized. A sand-box model system for describing photoisomerization processes is reported to demonstrate the usage of the software package. QSLE-v1.0 is open source and distributed under the GPLv2.0 license.

Tactfully regulating the ESIPT and TICT mechanism in the AIE-active multifunctional triphenylamine Schiff-base compound (TPASB) by methyl substitution

The triphenylamine Schiff-base (TPASB) with dual proton transfer sites (N1…H1–O1 [R1] and N2…H2–O2 [R2]), which is crucial in the field of optoelectronic materials. Herein, a novel molecular design strategy for preparing of TPASB-1 and TPASB-2 via the selective methylation of the hydroxyl group at the R2 or R1 position was proposed. The analysis of electronic structures and potential energy surfaces revealed that a single excited state intramolecular proton transfer (ESIPT) process of TPASB occurs only at R1. Nevertheless, the ESIPT process of TPASB-2 was successfully turned on at R2. More noteworthy is that compared to TPASB, the methylation of hydroxyl group at the R2 position triggers the TICT process of TPASB-1, effectively reducing the potential barrier of ESIPT at the R1 position. This theoretical study explains the role of the substituent effect in regulating ESIPT behaviour, and provides valuable guidance for synthesising efficacious ESIPT-active compounds.

Quantum phase structural stability and switching in twist-graphenes

This study examines the electronic structure and potential energy surfaces of migration paths in various types of bilayer graphene. Using periodic boundary conditions, density functional theory (DFT), and the generalized gradient approximation (GGA) exchange–correlation functional, along with the nudged elastic band (NEB) method, to investigate the structural stability and dynamic equilibrium of twisted bilayer graphenes (TBGs) with twist angles of 13.2° and 21.8°. The results suggest that twist angles significantly impact atomic and electronic properties, including moiré patterns, superlattice periods, and interfragment distances, which in turn influence bilayer graphene strongly correlated electronic quantum states. This research elucidates the fundamental mechanisms of superlubricity and mutual migration pathways of graphene fragments in TBGs. The low migration barriers observed could facilitate transitions between different energy-related phases, which are determined by the lattice moiré patterns and the localization character of the electronic states, resulting in superlubricity. External mechanical factors may affect the quantum properties of TBGs, indicating potential applications in quantum computing and quantum sensing.

Effects of Nanowire Doping on Plasmon-Enhanced N2 Dissociation.

Doping a transition metal element into plasmonic systems can tune the optical properties of the system, which will potentially facilitate the plasmon-enhanced catalytic process. In this study, we applied the linear-response time-dependent density functional theory (LR-TDDFT) method with real-time electron dynamics and mean-field Ehrenfest dynamics methods to computationally investigate the effects of doping silver nanowires on plasmon-enhanced N2 dissociation. We calculated the absorption spectra for different doped systems, applied an external electric field to the system, and performed mean-field Ehrenfest dynamics to examine how plasmonic excitation will affect the N2 activation or dissociation. In addition, we also studied how the transition metal dopant affects the system's electronic structure and potential energy surface.

Classical and quantum light-induced non-adiabaticity in molecular systems

The exchange of energy between electronic and nuclear motion is the origin of non-adiabaticity and plays an important role in many molecular phenomena and processes. Conical intersections (CIs) of different electronic potential energy surfaces lead to the most singular non-adiabaticity and have been intensely investigated. The coupling of light and matter induces conical intersections, which are termed light-induced conical intersections (LICIs). There are two kinds of LICIs, those induced by classical (laser) light and those by quantum light like that provided by a cavity. The present work reviews the subject of LICIs, discussing the achievements made so far. Particular attention is paid to comparing classical and quantum LICIs, their similarities and differences and their relationship to naturally occurring CIs. In contrast to natural CIs, the properties of which are dictated by nature, the properties of their light-induced counterparts are controllable by choosing the frequency and intensity (or coupling to the cavity) of the external light source. This opens the door to inducing and manipulating various kinds of non-adiabatic effects. Several examples of diatomic and polyatomic molecules are presented covering both dynamics and spectroscopy. The computational methods employed are discussed as well. To our opinion, the young field of LICIs and their impact shows much future potential.

Theoretical Investigation on Electronic Excited States of the HSO Radical.

HSO radicals play an important role in the photochemical processes in combustion, the atmosphere, and the interstellar medium. In this work, we perform a high-level ab initio study on the electronic excited states of HSO using the internally contracted multireference configuration interaction methods including Davidson correction (icMRCI + Q) in combination with the correlation-consistent basis sets. The molecular geometries, vertical transition energies, oscillator strengths, and electronic configurations of 19 electronic states of HSO are computed. The electronic potential energy curves of HSO along the bond lengths and bond angles are presented. Based on our calculations, the interactions between the electronic states involved in the ultraviolet region and the mechanism of photodissociation are discussed, which will lay a foundation for revealing the dissociation dynamics of gas-phase HSO molecules in outer space and the earth's atmosphere.

Beyond MD17: the reactive xxMD dataset

System specific neural force fields (NFFs) have gained popularity in computational chemistry. One of the most popular datasets as a bencharmk to develop NFF models is the MD17 dataset and its subsequent extension. These datasets comprise geometries from the equilibrium region of the ground electronic state potential energy surface, sampled from direct adiabatic dynamics. However, many chemical reactions involve significant molecular geometrical deformations, for example, bond breaking. Therefore, MD17 is inadequate to represent a chemical reaction. To address this limitation in MD17, we introduce a new dataset, called Extended Excited-state Molecular Dynamics (xxMD) dataset. The xxMD dataset involves geometries sampled from direct nonadiabatic dynamics, and the energies are computed at both multireference wavefunction theory and density functional theory. We show that the xxMD dataset involves diverse geometries which represent chemical reactions. Assessment of NFF models on xxMD dataset reveals significantly higher predictive errors than those reported for MD17 and its variants. This work underscores the challenges faced in crafting a generalizable NFF model with extrapolation capability.

Harmonic and anharmonic studies on THz spectra of two vanillin polymorphs

Polymorphism commonly exists in organic molecular crystals. The fingerprint features in low-frequency vibrational range are important information reflecting different intermolecular interactions of polymorphs. Interpreting these features is very helpful to understand vibrational property of polymorphs and reveal the thermodynamic stability. In this work, the low-frequency vibrations of form I and II of vanillin are investigated using terahertz time-domain spectroscopy. Static DFT calculation and ab initio molecular dynamics (AIMD) are employed to interpret their low-frequency vibrations of both forms in harmonic and anharmonic ways, respectively. Their low-frequency vibration characteristics in harmonic calculations are discussed, and anharmonic mode couplings between OH bond stretch and the stretching and bending motion of hydrogen bonds are uncovered. Moreover, the thermodynamic energies including electronic potential energy and vibrational/kinetic energy arising from nuclear motions are calculated. The result reveals that the stability order of the two forms is mainly dependent on their electric potential energy difference.

Quantum fundaments of catalysis: true electronic potential energy.

Catalysis is a quantum phenomenon enthalpically driven by electronic correlations with many-particle effects in all of its branches, including electro-photo-catalysis and electron transfer. This means that only probability amplitudes provide a complete relationship between the state of catalysis and observations. Thus, in any atomic system material), competing space-time electronic interactions coexist to define its (related) properties such as stability, (super)conductivity, magnetism (spin-orbital ordering), chemisorption and catalysis. Catalysts, reactants, and chemisorbed and transition states have the possibility of optimizing quantum correlations to improve reaction kinetics. Active sites with closed-shell orbital configurations share a maximum number of spin-paired electrons, mainly optimizing coulombic attractions and covalency and defining weakly correlated closed-shell (WCCS) structures. However, in compositions with open-shell orbital configurations, at least, quantum spin exchange interactions (QSEIopenshells) arise, stabilising unpaired electrons in less covalent bonds and differentiating non-weakly (or strongly) correlated open-shell (NWCOS) systems. In NWCOS catalysts, electronic ground states can have bonds with diverse and rival spin-orbital orderings as well as ferro-, ferri- and multiple antiferro-magnetic textures, which deeply define their activities. Particularly in inter-atomic ferromagnetic (FM) bonds, the increase in relevance of non-classical quantum potentials can significantly optimize chemisorption energies, transition states (TSs), activation energies (overpotential) and spin-dependent electron transfer (conductivity), overall implying the need for explaining the thermodynamic and kinetic origin of catalysis from its true quantum electronic energy. To do so, we use the connection between the Born-Oppenheimer approximation and Virial theorem in the treatment of electronic kinetic and potential energies. Thus, the exact fundamental interactions that decompose TSs appear. The possibility of increasing the stabilization of TSs, due to quantum correlations on NWCO catalysts, opens the possibility of simultaneously reducing chemisorption enthalpies and activation barriers of reaction mechanisms, which implies the anticipation and explanation of positive deviations from the Brønsted-Evans-Polanyi principle.

NATURAL ELECTROMAGNETIC MODES OF A COMPOSITE OPEN STRUCTURE INVOLVING A PERFECTLY CONDUCTING STRIP GRATING, AN INHOMOGENEOUS FERRITE LAYER, AND A MONOLAYER OF GRAPHENE

Subject and Purpose. Сonsidered are the natural modes and their correspondent eigenfrequencies of a composite structure which is nonuniform along one of the coordinates and consists of a lossy ferromagnetic layer placed in a static magnetic field. The layer involves a perfectly conducting strip grating at one of its boundaries and a graphene monolayer at the other. Methods and Methodology. The above stated problem can be approached within the analytical regularization procedure developed for dual series equations. The latter concern a broad class of diffraction problems which include, in particular, the diffraction of monochromatic plane waves on strip gratings placed at the boundary of a gyromagnetic medium. The amplitudes of the electromagnetic eigenmodes can be obtained from the infinite set of homogeneous linear algebraic equations solvable within a truncation technique. The roots of the system’s determinant represent complex-valued eigenfrequencies of the system under investigation. The material parameters adopted in our computations for the ferromagnetic layer correspond to such of yttrium iron garnet. Results. A number of numerical programs have been developed which permit analyzing the dependences of wave field eigenfunctions and complex eigenfrequencies upon geometrical parameters of the structure (such as grating slot width and period, and thickness of the lossy layer), as well as on electrodynamic parameters of the ferromagnet and graphene characteristics, specifically the chemical potential and relaxation energy of electrons. A number of behavioral regularities have been established, as well as the effect of non-uniformity of ferrite layer parameters upon the structure’s eigenfrequencies and wave field eigenfunctions. Conclusions. The structure under study has been shown to be is an open oscillatory system with a set of complex-valued natural frequencies demonstrating finite points of accumulation. The real parts of these eigenfrequencies lie in a certain interval determined by characteristic frequencies of the ferrite layer, while the imaginary parts are negative, such that the correspondent natural modes show an exponential decay with time. The grating edges represent the mirrors which the natural surface oscillations are reflected from, being supported at that by the ferromagnetic medium. The results obtained in this paper can be useful for creating the elemental base for microwave devices and the devices themselves.

Quantum and statistical state-to-state studies of cold Ar + H2+ collisions.

In this work we present new state-to-state integral scattering cross sections and initial-state selected rate coefficients for the 36Ar (1S) + H2+ (X2Σg+,v = 0,j) reactive system for collision energies up to 0.1 eV (with respect to the 36Ar (1S) + H2+ (X2Σg+,v = 0,j = 0) channel). To the best of our knowledge, these cross sections are the first fully state resolved ones that were obtained by performing time-independent quantum mechanical and quantum statistical calculations. For this purpose a new full-dimensional ground state 2A' adiabatic electronic potential energy surface was calculated at the MRCI+Q/aug-cc-pVQZ level of theory, which was fitted by means of machine learning methods. We find that a statistical quantum method and a statistical adiabatic channel model reproduce quantum mechanical initial-state selected cross sections fairly well, thus suggesting that complex-forming mechanisms seem to be playing an important role in the reaction dynamics of the reaction that was studied.

Quantification of hydrogen bond energy based on equations using spectroscopic, structural, QTAIM-based, and NBO-based descriptors which calibrated by the molecular tailoring approach

ContextHydrogen bonds critically influence the structure and properties of both organic molecules and biomolecules, as well as supramolecular assemblies. For this reason, the development and elaboration of methods for quantitative assessment of hydrogen bond energy is an urgent challenge. In this study, using a large series of hydroxycarbonyl aliphatic compounds with the O‒H···O = C intramolecular hydrogen bond, a bank of hydrogen bond descriptors was created, including spectroscopic, structural, QTAIM-based, and NBO-based parameters. It was shown that the O‒H vibration frequency, OH chemical shift as the spectroscopic descriptors, the O···H hydrogen bond length, O···O distance, and O‒H covalent bond length as the structural descriptors, the electron density and its Laplacian, electron potential energy density in the hydrogen bond critical point, the electron density at the ring critical point as the QTAIM-based descriptors change in a correlated manner. The same correlation is found in change of the charge transfer energy through a hydrogen bond, the occupancy of the O‒H bond antibonding orbital, the Wiberg indices of the O···H hydrogen bond, and the O‒H covalent bond, as well as the polarization of the O‒H bond, which are the NBO-based descriptors. It was also recognized that the specified descriptors from the spectroscopic, structural, QTAIM-based, and NBO-based categories are functionally related to the values of intramolecular hydrogen bond energy, quantified via the molecular tailoring approach. This allowed one to obtain a system of equations for quantitative estimation of intramolecular hydrogen bond energy based on the spectroscopic, structural, QTAIM, and NBO descriptors, which makes such quantification more dependable and reliable.MethodsTo obtain the spectroscopic descriptors, the vibrational spectra and shielding constants were calculated using the GIAO method. Structural descriptors were obtained for the equilibrium geometry of molecules, calculated at the MP2(FC)/6–311 + + (2d,2p) level using the Gaussian 09 program. The QTAIM-based descriptors were calculated using the AIMAll program within the framework of the quantum theory “Atoms in Molecules.” The NBO-based descriptors were calculated using the NBO 3.1 program implemented into Gaussian 09. To quantify the energy of intramolecular hydrogen bonds, molecular fragmentation was used within the molecular tailoring approach.

Combined Quantum Mechanical and Quasi-Classical State-to-State Dynamical Study on the Isotopic Effect in H/D + LiH+/LiD+ → H2/HD/D2 + Li+ Reactions.

Coriolis-coupled quantum mechanical (QM-CC) and quasi-classical trajectory (QCT) calculations are carried out to investigate the dynamics of the H(D) + LiH+(v = 0, j = 0) → H2(HD) (v', j') + Li+ reactions on the ground electronic state potential energy surface reported by Martinazzo et al. (Martinazzo et al., J. Chem. Phys. 2003, 119, 11241). The QM-CC and QCT results at the initial state-selected and state-to-state levels are used to investigate the validity and accuracy of the QCT method for these exoergic barrierless reactions. Furthermore, the QCT method is used to understand the isotopic effects on reaction observables like total and state-to-state integral cross section, differential cross section, product energy disposal, and rate constants of H(D) + LiH+(v = 0, j = 0) → H2(HD) (v', j') + Li+ and H(D) + LiD+(v = 0, j = 0) → HD(D2) (v', j') + Li+ reactions. Attempts are also made to understand the impact of the isotopic substitution on the reaction mechanism. It is observed that QM-CC and QCT results closely follow each other at the initial state-selected and state-to-state levels. Noticeable kinematic effects of reagents on the reactivity and mechanism of the reactions are also observed.

Self-assembly of macrocyclic oligofurans to create novel organic nanotubes through π–π stacking: a computational study

ABSTRACT In this manuscript, the potential utility of 6CF macrocyclic oligofuran is theoretically investigated to create novel nanotubes. The energetic, electronic, structural and topological properties of π-stacked systems are examined at B3LYP/6-31 + G(d), wB97XD/6-31 + G(d) and M06-2X/6-31 + G(d) levels of theory. The findings indicate that the self-assembly of 6CF macrocyclic oligofurans can be considered to create organic nanotubes through π–π stacking. The strength and nature of π-π interactions are examined using the atoms in molecules (AIM) approach. Meaningful relationships are obtained between stability, electronic properties and the number of stacked π-conjugated macrocyclic oligofurans. The stability and polarisability of π-stacked systems are amplified by increasing number of macrocycles. Reverse behaviours are found for the values of band gap, electronic chemical potential and first ionisation energy.

Inelastic scattering of Li＋ with CO: New ab initio potential energy surface and quantum dynamics

The interaction potential between Li＋ and CO has been investigated using quantum dynamical calculations. The ab initio ground electronic potential energy surface has been computed using the aug-cc-pVQZ basis set at MRCI level of accuracy. Quantum dynamics results within the VCC-RIOSA framework have been presented at collision energy Ec.m. = 3.64 eV. The computed differential cross sections (DCS) for the inelastic vibrational excitations have been found to be in qualitative agreement with those obtained in the experiments of Böttner et al. (1976). Other attributes like rotationally-summed state-to-state DCS, and integral cross sections, are also calculated. The rotational excitations are studied using rigid-rotor coupled-states methodology at Ec.m. = 4.23 eV showing excitations up to j′ = 40. Rotational excitations rates at very low collision energy range (Ec.m. = 0–300 cm−1) using rigid-rotor full close-coupling method have also been calculated in view of their astrophysical significance.

Electron interaction with point defects in CdSe0.35Te0.65: joining of ab initio approach with short-range principle

This study examines the problem of influence of point defects on transport phenomena in CdSexTe1-x (x=0.35) crystals. For the first time, the calculation of the electronic spectrum, wave function and potential energy of the electron in CdSe0.35Te0.65 samples at a prearranged temperature was carried out. Using the supercell method, the types of point defects were established, as well as the temperature dependence of their ionization energies in the studied temperature range. The temperature dependences of the deformation constants of the optical and acoustic scattering potentials were detected and also calculated the dependences on temperature of electron scattering constants on different crystal point defects. Temperature dependences of the mobility and Hall factor of electrons were found based on the scattering models on the short-range potential.

Primary and Secondary Processes in the Ultraviolet Photodissociation of CpCo(CO)2 (Cyclopentadienylcobalt Dicarbonyl).

We investigated the photodissociation dynamics of CpCo(CO)2 (cyclopentadienylcobalt dicarbonyl) in metal-to-ligand charge transfer (MLCT) bands. By employing DFT calculations, the absorption band (210-240 nm) was characterized as a charge transfer from the Co center to the Cp (cyclopentadienyl, C5H5) ligand. Ion imaging was utilized to analyze the CO fragments and coordinatively unsaturated complexes (CpCoCO, CpCo, and CoC3H3) across the entire MLCT band. Measuring the production yields of individual unsaturated complexes as a function of photolysis wavelength by considering wavelength dependence indicated the involvement of several photochemical pathways: the first photodissociation and sequential dissociation of CpCo(CO)2, and the second photodissociation of unsaturated intermediates within the pulse duration of the photolysis laser. The recoil velocity shifts of CpCo and CoC3H3 were attributed to the onset of the sequential dissociation of CpCoCO. Evidence for the second photodissociation of CpCoCO was obtained through the matching of linear momenta between the CO(v = 0, 1) and CpCo fragments. The DFT calculations performed to determine the electronic structures and potential energy curves for photoinduced CO loss in CpCo(CO)2 and CpCoCO supported our interpretation of the experimental results. This study presents a practical approach to selectively detecting specific processes among the mixture of products and intermediates when photolyzing transition-metal carbonyls, as their concurrent generation is unavoidable in laser-based experiments.

Machine Learning Representations of the Three Lowest Adiabatic Electronic Potential Energy Surfaces for the ArH2+ Reactive System.

In this work, we present Gaussian process regression machine learning representations of the three lowest coupled 2A' adiabatic electronic potential energy surfaces of the ArH2+ reactive system in full dimensionality. Additionally, the nonadiabatic coupling matrix elements were calculated. These adiabatic potentials and their nonadiabatic couplings are necessary ingredients in the theoretical investigation of the nonadiabatic reaction dynamics of the Ar + H2+ → ArH+ + H and Ar+ + H2 → ArH+ + H reactions, as well as the competing charge transfer process, Ar + H2+↔ Ar+ + H2. Accurate ab initio electronic structure calculations (ic-MRCI+Q/aug-cc-pVQZ), whereby the effect of spin-orbit coupling in Ar+ has been accounted for through the state interaction method, serve as input for the machine learning training process. The potential energy surfaces are fitted with high accuracies, with root-mean-square errors on the order of 10-7 eV for the three surfaces, which meet the requirements for chemical dynamics at low temperature. It was found that quite a large number of training points (of the order of 5000 ab initio points) are needed in order to achieve these accuracies due to the complex topography of these electronic surfaces.

Electronic Structure, Spectroscopy, Cold Ion–Atom Elastic Collision Properties, and Photoassociation Formation Prediction of the (MgCs)+ Molecular Ion

In this paper, we extensively study the electronic structure, interactions, and dynamics of the (MgCs)+ molecular ion. The exchanges between the alkaline atom and the low-energy cationic alkaline earths, which are important in the field of cold and ultracold quantum chemistry, are studied. We use an ab initio approach based on the formalism of non-empirical pseudo-potential for Mg2+ and Cs+ cores, large Gaussian basis sets, and full-valence configuration interaction. In this context, the (MgCs)+ cation is treated as an effective two-electron system. Adiabatic potential energy curves and their spectroscopic constants for the ground and the first 20 excited states of 1,3Σ+ symmetries are determined. Furthermore, we identify the avoided crossings between the electronic states of 1,3Σ+ symmetries. These crossings are related to the charge transfer process between the two ionic limits, Mg/Cs+ and Mg+/Cs. Therefore, vibrational-level spacings and the transition and permanent dipole moments are presented and analyzed. Using the produced potential energy data, the ground-state scattering wave functions and elastic cross-sections are calculated for a wide range of energies. In addition, we predict the formation of a translationally and rotationally cold molecular ion (MgCs)+ in the ground-state electronic potential energy through a stimulated Raman-type process aided by ion–atom cold collision. In the low-energy limit (<1 mK), elastic scattering cross-sections exhibit Wigner law threshold behavior, while in the high-energy limit, the cross-sections act as a function of energy E go as E−1/3. A qualitative discussion about the possibilities of forming cold (MgCs)+ molecular ions by photoassociative spectroscopy is presented.