Non-empirical INDO-MO calculations on some vanadium(IV) halides

ODIN, a non-empirical INDO-MO scheme, has been used to determine the ground state electronic configurations for the tetrahedral molecules, VCl₄ and VBr₄. A ² E ground state was obtained for both molecules. The Photoelectron spectrum and the electronic spectrum have been calculated for VCl₄, and a satisfactory correlation with the corresponding experimental data was made. Also, ODIN was employed to evaluate electronic transition energies and the photoelectron spectrum of VBr₄.     

Direct photoionization measurements of slow decay rates of vibrationally overexcited (CF3)3CI molecules in the ground electronic state in a beam

A direct photoionization technique is proposed to measure the dissociation rates of overexcited polyatomic iodides in the ground electronic state. Measurements are carried out in a molecular beam, which enables one to avoid thermal drift of the reagents and thus widen the range of the measurements toward longer lifetimes. Here the first results are reported of measurement of unimolecular decay rates of (CF₃)₃CI whose overexcitation in the electronic ground state has been effected by the IR multiple-photon excitation technique.     

Calculations of the electronic states of the HgI and HgTe molecules by the SCF-Xα-SW method

The SCF-X_α-SW method was used to study the electronic structure and calculate the spectroscopic constants of the HgI and HgTe molecules in the ground and excited electronic states.     

Quantum control spectroscopy of vibrational modes: Comparison of control scenarios for ground and excited states in β-carotene

Quantum control spectroscopy (QCS) is used as a tool to study, address selectively and enhance vibrational wavepacket motion in large solvated molecules. By contrasting the application of Fourier-limited and phase-modulated excitation on different electronic states, the interplay between the controllability of vibrational coherence and electronic resonance is revealed. We contrast control on electronic ground and excited state by introducing an additional pump beam prior to a DFWM-sequence (Pump-DFWM). Via phase modulation of this initial pump pulse, coherent control is extended to structural evolution on the vibrationally hot ground state (hot-S₀) and lowest lying excited state (S₁) of β-carotene. In an open loop setup, the control scenarios for these different electronic states are compared in their effectiveness and mechanism.     

Molecular Structure,Thermodynamic and Spectral Characteristics of Metal-Free and Nickel Complex of Tetrakis(1,2,5-thiadiazolo)porphyrazine

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H₂TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H₂TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D_2h and D_4h symmetry was obtained for H₂TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state ¹A_1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H₂TTDPz and NiTTDPz were studied experimentally and simulated theoretically.     

A new approach to calculations of intensities of vibrational overtone transitions

A new approach to the theory of intensities of vibrational overtone transitions is formulated in terms of vibrational coupling of the molecular ground state to excited electronic states. Model calculations indicate an important role of nuclear geometry of the excited electronic states in determining overtone spectra. It is shown that the observed overtone spectrum of the CH stretching mode in benzene can be reproduced theoretically with the assumption that CH bond lengths in the e_lu electronic state are shortened relative to the ground configuration. A simple rule for qualitative prediction of the overtone spectra for diatomic molecules is proposed.     

Thermodynamic functions for vibronic systems

A method is introduced which simplifies the derivation of equations for the calculation of statistical sums for vibronic systems. Within the “independent ordering approximation” analytical expressions are found for thermodynamic functions for molecules with degenerate electronic ground state (E?β and E ? e types of degeneracies). Vibronic interactions are shown to yield an additional thermodynamic stabilization. The computations were carried out for VCl₄ and VBr₄ with doubly degenerate electronic ground states. For these molecules the effect is shown to be small.     

An ab initio study of ground state, electronic and thermodynamical properties of GaP and Ga2P

In the present paper, we report an ab initio calculation of the ground state, electronic and thermodynamical properties like constant volume lattice specific heat, vibrational energy, internal energy, and entropy for GaP and Ga₂P is presented. These properties are obtained after calculating the phonon spectrum over the entire Brillouin zone. The calculations were performed using the ABINIT program package, which is based on density functional theory (DFT) method and the use of pseudopotentials and plane wave expansion. Difference in the ground state properties such as electronic structure and thermodynamical properties are discussed. The thermodynamical properties follow the expected trend. There is a good agreement between present theoretical and limited available experimental data in the case of ground state such as lattice constant and bulk modulus and electronic properties. With the increase of Ga atoms in the unit cell the semiconducting nature of Ga₂P turns to metallic. There is a noticeable difference in the thermodynamical properties in the case of both gallium compounds.     

Does He2 Exist?

For the electronic ground state X ¹Σ⁺_g, the potential-energy function of He₂ reported by Aziz et al. has been transformed into the form V(z), containing only eight parameters, which is more suitable for the investigation of the existence of states of discrete energy. We found no evidence that a bound vibration-rotational state of the stable diatomic molecule ³He₂ or ⁴He₂, even if rotating, can exist in the electronic ground state.     

Ground and Electronically Excited Singlet‐State Structures of 5‐Fluoroindole Deduced from Rotationally Resolved Electronic Spectroscopy and ab Initio Theory

The structure and electronic properties of the electronic ground state and the lowest excited singlet state (S₁) of 5‐fluoroindole (5FI) were determined by using rotationally resolved spectroscopy of the vibration‐less electronic origin of 5FI. From the parameters of the axis reorientation Hamiltonian, the absolute orientation of the transition dipole moment in the molecular frame was determined and the character of the excited state was identified as L_b.     

Theoretical calculations and vibrational spectra of 1,4-benzodioxan in its S(1)(pi, pi*) electronic excited state

The structure and vibrational frequencies of 1,4-benzodioxan in its S₁(π, π^*) electronic state have been calculated using the GAUSSIAN 03 and TURBOMOLE programs. The results have been compared to experimental data and also to the ground state. Structural data for the T₁(π, π^*) state have also been calculated. The theoretical frequencies agree very well with the experimental values for the S₀ electronic ground state but are less accurate for the S₁ excited state. Nonetheless, they provide valuable guidance for excited state calculations.     

Ab initio study of the ground and lower-lying excited electronic states of NiX2 and FeX2 (X=F,Cl, Br,I) molecules

The ground and lower-lying excited electronic states of FeX₂ and NiX₂ (X=F, Cl, Br, I) molecules are systematically investigated by ab initio method at the complete active space self-consistent field (CASSCF) and multiconfigurational quasi-degenerate second-order perturbation (MCQDPT2) levels of theory. It is concluded that the dynamic electron correlation has to be taken into account in the prediction of the properties for such kind of molecules. The equilibrium bond lengths r_e(M–X), force constants and harmonic vibrational frequencies are calculated for the ground and lower-lying excited electronic states. The spin-orbit coupling (SOC) effects are analysed.     

Beryllium Atom Mediated Dinitrogen Activation via Coupling with Carbon Monoxide

The reactions of laser‐ablated beryllium atoms with dinitrogen and carbon monoxide mixtures form the end‐on bonded NNBeCO and side‐on bonded (η²‐N₂)BeCO isomers in solid argon, which are predicted by quantum chemical calculations to be almost isoenergetic. The end‐on bonded complex has a triplet ground state while the side‐on bonded isomer has a singlet electronic ground state. The complexes rearrange to the energetically lowest lying NBeNCO isomer upon visible light excitation, which is characterized to be an isocyanate complex of a nitrene derivative with a triplet electronic ground state. A bonding analysis using a charge‐ and energy decomposition procedure reveals that the electronic reference state of Be in the NNBeCO isomers has an 2s⁰2p² excited configuration and that the metal‐ligand bonds can be described in terms of N₂→Be←CO σ donation and concomitant N₂←Be→CO π backdonation. The results demonstrate that the activation of N₂ with the N?N bond being completely cleaved can be achieved via coupling with carbon monoxide mediated by a main group atom.     

Calculations on 1,8-naphthoquinone predict that the ground state of this diradical is a singlet

(12/12)CASPT2, (16/14)CASPT2, B3LYP, and CCSD(T) calculations have been carried out on 1,8-Naphthoquinone (1,8- NQ ), to predict the low-lying electronic states and their relative energies in this non-Kekulé quinone diradical. CASPT2 predicts a ¹A₁ ground state, with three other electronic states—³B₂, ³B₁, and ¹B₁—within about 10 kcal/mol of the ground state in energy. On the basis of the results of these calculations, it is predicted that NIPES experiments on 1,8- NQ ^•– will find that 1,8- NQ is a diradical with a singlet ground state. © 2018 Wiley Periodicals, Inc.     

Use of the distance/similarity measure for estimating local aromaticity in benzeneoid hydrocarbons

The distance/similarity¹ between an individual benzene ring in a benzeneoid hydrocarbon and benzene itself, with respect to their electronic structure, is used to define a new local aromaticity index. The electronic structure in ground and excited state is assumed to be adequately represented by the charge-bond order matrix calculated in a LCAO-MO quantum chemical approximation. The overall correctness of the index is verified for the ground state, but it should be especially useful for estimating the (S₁)-excited-state-benzene character of benzeneoid rings in excited molecules.     

Einzentrenmodell für die Clusterverbindung [Nb6Cl12]4+

The electronic ground state of [Nb₆Cl₁₂]⁴⁺ is calculated using a one-center-model. One obtains the observed diamagnetic character.     

Molecular electric properties in electronic excited states: multipole moments and polarizabilities of H2O in the lowest1 B 1 and3 B 1 excited states

Summary The dipole and quadrupole moments and the dipole polarizability tensor components are calculated for the¹ B ₁ and³ B ₁ excited states of the water molecule by using the complete active space (CAS) SCF method and an extended basis set of atomic natural orbitals. The dipole moment in the lowest¹ B ₁ (0.640 a.u.) and³ B ₁ (0.416 a.u.) states is found to be antiparallel to that in the ground electronic state of H₂O. The shape of the quadrupole moment ellipsoid is significantly modified by the electronic excitation to both states investigated in this paper. All components of the excited state dipole polarizability tensor increase by about an order of magnitude compared to their values in the ground electronic state. The present results are used to discuss some aspects of intermolecular interactions involving molecules in their excited electronic states.     

Theoretical electronic studies of aluminum monobromide and aluminum monoiodide

By using CASSCF/MRCI methods, theoretical molecular calculations have been performed for 12 electronic states for AlBr molecule and 12 electronic states for AlI molecule in the representation ^2s+1Λ (neglecting spin‐orbit effects). Calculated potential energy curves are displayed. Spectroscopic constants including the harmonic vibrational wave number ω_e, the electronic energy T_e referred to the ground state and the equilibrium internuclear distance R_e are predicted for these singlet and triplet electronic states for both AlBr and AlI molecules. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Control of the Electronic Ground State on an Electron‐Transfer Copper Site by Second‐Sphere Perturbations

The Cu_A center is a dinuclear copper site that serves as an optimized hub for long‐range electron transfer in heme–copper terminal oxidases. Its electronic structure can be described in terms of a σ_u* ground‐state wavefunction with an alternative, less populated ground state of π_u symmetry, which is thermally accessible. It is now shown that second‐sphere mutations in the Cu_A containing subunit of Thermus thermophilus ba₃ oxidase perturb the electronic structure, which leads to a substantial increase in the population of the π_u state, as shown by different spectroscopic methods. This perturbation does not affect the redox potential of the metal site, and despite an increase in the reorganization energy, it is not detrimental to the electron‐transfer kinetics. The mutations were achieved by replacing the loops that are involved in protein–protein interactions with cytochrome c, suggesting that transient protein binding could also elicit ground‐state switching in the oxidase, which enables alternative electron‐transfer pathways.     

Potential energy curves and spectral properties for electronic states of F2 and F+2

Potential energy (PE) curves for the Rydberg states of F₂, and for the ground and lowest two electronic states each of symmetry ²Π_g,u, ²Δ_g,u and ²Σ^±_g,u of F⁺₂, have been obtained using modest-sized configuration-interaction calculations. These PE curves have been used to calculate spectroscopic constants for the electronic states and the results agree reasonably well with the limited experimental and theoretical results previously reported. The theoretical PE curves for the Rydberg states of F₂ are found to be strongly perturbed by valence-Rydberg-ionic interactions and these perturbations appear to be responsible for certain features in recently reported electron energy-loss spectra in F₂. The corresponding electronic wavefunctions have been used to calculate the electronic transition moment, as a function of the internuclear distance, for dipole-allowed transitions between the lowest excited electron state of each symmetry and the appropriate ground electronic state. The radiative emission probabilities, natural lifetimes, and absorption oscillator strengths, for each band system, are also reported here. The predicted lifetimes for vibrational levels of the A ²Π_u of electronic state in F⁺₂ vary from 1.3–1.5 μs and agree reasonably well with the single available set of measurements. The predicted radiative lifetimes for the higher electronic states of F⁺₂ are substantially longer and fall into the range 5–100 ms.