Journal of Physical Chemistry. A

We present a systematic experimental analysis of the 1:1 complex of 2,7-diazaindole (27DAI) with water in the gas phase. The complex was characterized by using two-color-resonant two-photon ionization (R2PI), laser-induced fluorescence (LIF), single vibronic level fluorescence (SVLF), and photoionization efficiency (PIE) spectroscopic methods. The 00 0 band of the S1 ←S0 electronic transition of the 27DAI-H2 O complex was observed at 33,074 cm-1 , largely red-shifted by 836 cm-1 compared to that of the bare 27DAI...

Biomass reburning is an efficient and low-cost way to control nitric oxide (NO), and the abundant potassium (K) element in biomass affects the heterogeneous reaction between NO and biochar. Due to the incomplete simulation of the NO heterogeneous reduction reaction pathway at the molecular level and the unclear catalytic effect of K element in biochar, further research is needed on the possible next reaction and the influencing mechanism of the element. After the products of the existing reaction pathways are referenced, two reasonably simplified biochar structural models are selected as the basic reactants to study the microscopic mechanism for further NO heterogeneous reduction on the biochar surface before and after doping with the K atom based on density functional theory...

An operator formulation of centroid molecular dynamics (CMD) for rotational degrees of freedom is presented. The quasi-density operator concept was introduced by Jang and Voth [J. Chem. Phys 111 , 2357 (1999)] and is used to obtain a phase-space mapping without the need for discretized path integrals. The approach allows the calculation of approximate Kubo-transformed time correlation functions. The particle on a ring is chosen as an illustrative example. Numerical results demonstrate that the proposed approach leads to accurate results when compared with exact diagonalization calculations for linear operators...

Despite being an important closo -borate in condensed phase boron chemistry, isolated [B10 H10 ]2- is electronically unstable and has never been detected in the gas phase. Herein, we report a successful capture of this fleeting species through binding with an octamethylcalix[4]pyrrole (omC4P) molecule to form a stable gaseous omC4P·[B10 H10 ]2- complex and its characterizations utilizing negative ion photoelectron spectroscopy (NIPES). The recorded NIPE spectrum, contributed by both omC4P and [B10 H10 ]2- , is deconvoluted by subtracting the omC4P contribution to yield a [B10 H10 ]2- spectrum...

We propose a new perturbation theory framework that can be used to help with the projective solution of the Schrödinger equation for arbitrary wave functions. This Flexible Ansatz for N -body Perturbation Theory (FANPT) is based on our previously proposed Flexible Ansatz for the N -body Configuration Interaction (FANCI). We derive recursive FANPT expressions, including arbitrary orders in the perturbation hierarchy. We show that the FANPT equations are well-behaved across a wide range of conditions, including static correlation-dominated configurations and highly nonlinear wave functions...

We present a relativistic equation-of-motion coupled-cluster with single and double excitation formalism within the exact two-component framework (X2C-EOM-CCSD), where both scalar relativistic effects and spin-orbit coupling are variationally included at the reference level. Three different molecular mean-field treatments of relativistic corrections, including the one-electron, Dirac-Coulomb, and Dirac-Coulomb-Breit Hamiltonian, are considered in this work. Benchmark calculations include atomic excitations and fine-structure splittings arising from spin-orbit coupling...

Recently, pyrrole cages have been synthesized that encapsulate ion pairs and silver(I) clusters to form intricate supramolecular capsules. We report here a computational analysis of these structures using density functional theory combined with a semiempirical tight-binding approach. We find that for neutral pyrrole cages, the Gibbs free energies of formation provide reliable predictions for the ratio of bound ions. For charged pyrrole cages, we find strong argentophilic interactions between Ag ions on the basis of the calculated bond indices and molecular orbitals...

H2 S is being detected in the atmospheres of ever more interstellar bodies, and photolysis is an important mechanism by which it is processed. Here, we report H Rydberg atom time-of-flight measurements following the excitation of H2 S molecules to selected rotational ( J KaKc ') levels of the 1 B1 Rydberg state associated with the strong absorption feature at wavelengths of λ ∼ 129.1 nm. Analysis of the total kinetic energy release spectra derived from these data reveals that all levels predissociate to yield H atoms in conjunction with both SH(A) and SH(X) partners and that the primary SH(A)/SH(X) product branching ratio increases steeply with ⟨ J b 2 ⟩, the square of the rotational angular momentum about the b -inertial axis in the excited state...

As a typical thermally activated delayed fluorescence (TADF) emitter with green emission, 4CzIPN has attracted much attention recently. Most studies indicated that 4CzIPN doped in different hosts presented different performances; thus, the hosts should have an obvious influence on its photophysical properties. Herein, the influence of four kinds of hosts, including m-CzPym, m-CzTrz, p-CzPym, and p-CzTrz, on the photophysical properties of 4CzIPN is investigated. Molecular dynamics simulations were performed to simulate the host-guest conformations, and the photophysical properties were studied using the combined quantum mechanics/molecular mechanics method coupled with the thermal-vibration correlation function method...

The impact of non-Born-Oppenheimer couplings on the isotopic effects in the reaction of the Cl(2 P) atom with the HD ( v = 0, j = 0) molecule is investigated with our recently developed nonadiabatic time-independent quantum scattering methods, where the full open-shell characteristics are included in the six-state model, and also with the recently developed two-state model solving by time-independent methods, where part of the open-shell characteristic is included. The same reaction is also calculated with the simple adiabatic model using the lowest adiabatic potential energy surface...

A global diabatization scheme, based on the "valence-hole" concept, has been previously applied to model webs of avoided crossings that exist in four electronic-state symmetry manifolds of C2 (1 Πg , 3 Πg , 1 Σu + , and 3 Σu + ). Here, this model is extended to the electronically excited states of four more molecules: CN (2 Σ+ ), N2 (3 Πu ), SiC (3 Π), and Si2 (3 Πg ). Many strangenesses in the spectroscopic observations (e.g., energy level structure, predissociation linewidths, and radiative lifetimes) for all four electronic state systems discussed here are accounted for by this unified model...

Machine learning (ML) provides a great opportunity for the construction of models with improved accuracy in classical molecular dynamics (MD). However, the accuracy of a ML trained model is limited by the quality and quantity of the training data. Generating large sets of accurate ab initio training data can require significant computational resources. Furthermore, inconsistent or incompatible data with different accuracies obtained using different methods may lead to biased or unreliable ML models that do not accurately represent the underlying physics...

The metal-ligand charge transfer (3 MLCT) and phosphorescence-quenching metal-centered (3 MC) states of the helicate and mesocate diastereoisomers of a double-stranded dinuclear polypyridylruthenium(II) complex have been investigated using ultrafast transient absorption spectroscopy. At 294 K, transient signals of the helicate decayed significantly slower than those of the mesocate, whereas at 77 K, no clear contrast in kinetics was observed. Contributions to excited-state decay from high-lying 3 MLCT states were identified at both temperatures...

Herein, we report a computation study based on the density functional theory calculations to understand the mechanism and ligand effect of the base-stabilized dialumenes toward dihydrogen activation. Among all of the examined modes of dihydrogen activation using the base-stabilized dialumene, we found that the concerted 1,2-hydrogenation of the Al═Al double bond is kinetically more preferable. The concerted 1,2-hydrogenation of the Al═Al double bond adopts an electron-transfer model with certain asynchrony...

Predicting the melting temperature of materials has always been a topic of great concern. This article proposes an alternative model for determining the melting temperature of materials based on the main idea of the Lindemann melting criterion combined with the first-principles calculations of density functional theory. To verify the accuracy of the melting model, this article selected typical ionic crystals of MgO and 10 alkali metal halides as the validation objects. The calculation results indicate that the melting temperature of the MgO crystals and I-VII compounds is in good agreement with the experimental results...

Spectroscopic characterization of highly excited neutral transition-metal complexes is important for understanding the multifaceted reaction mechanisms between metals and ligands. In this work, the reactions of neutral chromium atoms with carbon monoxide were probed by size-specific infrared spectroscopy. Interestingly, Cr(CO)3 was found to have an unprecedented 7 A2 ″ septet excited state rather than the singlet ground state. A combination of experiment and theory shows that the gas-phase formation of this highly excited Cr(CO)3 is facile both thermodynamically and kinetically...

The H atom abstraction reactions from alkanes and alkenes by ṄH2 are decisive in predicting the combustion characteristics of NH3 /CxHy binary fuels. Theoretical investigation is carried out on the energy barriers of H atom abstraction reactions from C1-C4 alkanes/alkenes by ṄH2 radicals at the QCISD(T)/CBS//M06-2 X /6-311++G(d,p) level of theory. Single-point energies of each species are computed using QCISD(T)/cc-pVDZ, TZ level of theories with basis set corrections from MP2/cc-pVDZ, TZ, and QZ methods...

In this work, the discrimination of the enantiomers of cysteine (l- and d-CYS) using the chiral Au34 and Ag4 @Au30 clusters was theoretically investigated in the gas phase and water. Two modes were considered for the interaction of each enantiomer with the clusters (via only its S atom or its S atom and NH2 group, simultaneously). The interaction energy ( E int ) and adsorption energy ( E ad ) for the complexation of each enantiomer with the clusters for each interaction mode were calculated. Considering the calculated interaction energies, the interaction of d-CYS with Au34 is stronger than that of l-CYS with the same cluster...

The rotational spectra of two valine methyl ester (ValOMe) conformers have been measured using a cavity-based Fourier-transform microwave spectrometer in the range of 9-18 GHz. Ten conformers of ValOMe were modeled using the ωB97XD/6-311++G(d,p) level of theory, and separate spectra arising from two lowest-energy conformations were observed and assigned. 44 rotational transitions were assigned to conformer I, the lowest-energy configuration, and were fit to Watson's A -reduced Hamiltonian: A = 2552.0145(5) MHz, B = 1041...

The uniform semiclassical expression for the energy-dependent transmission probability through a barrier has been a staple of reaction rate theory for almost 90 years. Yet, when using the classical Euclidean action, the transmission probability is identical to 1/2 when the energy equals the barrier height since the Euclidean action vanishes at this energy. This result is generally incorrect. It also leads to an inaccurate estimate of the leading order term in an ℏ 2 n expansion of the thermal transmission coefficient...