Search results for "Open shell"

Ab initio calculations of structural, electronic and vibrational properties of BaTiO3 and SrTiO3 perovskite crystals with oxygen vacancies

2020

The first-principles (ab initio) computations of the structural, electronic, and phonon properties have been performed for cubic and low-temperature tetragonal phases of BaTiO3 and SrTiO3 perovskite crystals, both stoichiometric and non-stoichiometric (with neutral oxygen vacancies). Calculations were performed with the CRYSTAL17 computer code within the linear combination of atomic orbitals approximation, using the B1WC advanced hybrid exchange-correlation functional of the density-functional-theory (DFT) and the periodic supercell approach. Various possible spin states of the defective systems were considered by means of unrestricted (open shell) DFT calculations. It was demonstrated that…

Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad

2018

Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…

Quantum-chemical determination of Born–Oppenheimer breakdown parameters for rotational constants: the open-shell species CN, CO+ and BO

2013

The quantum-chemical protocol for computing Born-Oppenheimer breakdown corrections to rotational constants in the case of diatomic molecules is extended to open-shell species. The deviation from the Born-Oppenheimer equilibrium rotational constant is obtained by considering three contributions: the adiabatic correction to the equilibrium bond distance, the electronic contribution to the moment of inertia requiring the computation of the rotational g-tensor, and the so-called Dunham correction. Values for the Born-Oppenheimer breakdown parameters of CN, CO+, and BO in their (2)sigma(+) electronic ground states are reported based on coupled-cluster calculations of the involved quantities and …

Thermochemical properties of small open-shell systems: experimental and high-levelab initioresults for NH2and

2006

The first adiabatic ionization energy and the first singlet–triplet splitting of the amidogen radical (NH2) have been determined by high-level ab initio quantum chemistry based on the coupled-cluster approach (90 041 and 10 319 cm−1, respectively) and by high-resolution pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy (90 083.8 ± 1.0 and 10 222.0 ± 1.3 cm−1, respectively). A comparison between the theoretical and experimental values demonstrates the predictive powers of high-level ab initio theory in the derivation of the thermochemical properties of small molecular systems. The absolute accuracy of better than 100 cm−1 alleviates the experimental search for…

Assessment for the mean value total dressing method: Comparison with coupled cluster including triples methods for BF, NO+, CN+, C2, BeO, NH3, CH2, H…

1997

Limited previous experience with the mean value total dressing (MVTD) method had shown that MVTD energies for closed shell systems are generally better than CCSD(T) ones compared to FCI. The method, previously published as total dressing 2′(td-2′), is based on the single reference intermediate Hamiltonian theory. It is not a CC method but deals in a great part with the same physical effects that CC methods that incorporate amplitudes of triples such as CCSDT or its CCSDT-1n approaches. A number of test calculations comparing to diverse CC methods, as well as FCI and experiment when available, have been performed. The tests concern equilibrium energies in NH3 and CH2, equilibrium energies an…

Analytic first derivatives for a spin-adapted open-shell coupled cluster theory: Evaluation of first-order electrical properties

2014

An analytic scheme is presented for the evaluation of first derivatives of the energy for a unitary group based spin-adapted coupled cluster (CC) theory, namely, the combinatoric open-shell CC (COSCC) approach within the singles and doubles approximation. The widely used Lagrange multiplier approach is employed for the derivation of an analytical expression for the first derivative of the energy, which in combination with the well-established density-matrix formulation, is used for the computation of first-order electrical properties. Derivations of the spin-adapted lambda equations for determining the Lagrange multipliers and the expressions for the spin-free effective density matrices for…

Application of the open-shell size-consistent self-consistent singles and doubles configuration interaction method to multielectronic transitions in …

2000

The size-consistent self-consistent matrix dressing method has been applied on an open-shell single-configuration reference state. Once the reference state is converged, several low-lying roots can be obtained for the dressed configuration interaction (CI) matrices of appropriate symmetry. The CI matrices were built with a complete-active-space singles and doubles CI method in order to deal properly with multiconfiguration excited states. The vertical ionization and ionization–excitation transitions are obtained from the difference to the closed shell ground-state energy of the neutral molecule. The method has been applied to NH+3 and N+2 using atomic natural orbital basis sets and state-av…

A Discussion of Some Problems Associated with the Quantum Mechanical Treatment of Open-Shell Molecules

2003

General occurrence of polar twisted minima in the ionic singlet excited surfaces of polyenes

1982

Except for a few cases, the lowest closed shell SCF solutions for the twisted geometries of polyenes involves delocalized nonpolarized MO’s, and represents a meaningless mixture of radicalar gound state and ionic excited states. Higher (quasi) solutions allow a realistic approach of the polarized ionic states. Orthogonality to the radicalar ground state may be imposed without important loss of energy. Further extensive CI does not modify significantly the situation. These statements are illustrated through ab initio calculations of butadiene and hexatriene. This approach allows us to show that slight distortions stablize polar minima even in ’’homosymmetric’’ molecules such as all‐trans hex…

About the evaluation of the local kinetic, potential and total energy densities in closed-shell interactions

2001

Abstract The local kinetic G( r ) , potential V( r ) and total E( r ) energy densities, calculated at the critical points of 37 H⋯F closed-shell interactions by quantum mechanical methods, have been compared to their estimated values obtained by using an approximate evaluation of G( r ) and the local form of the virial theorem. The results presented here show very small differences between the corresponding quantities, and therefore support the validity of the estimations. Thus, the equations used in this procedure provide useful information for topological studies of experimental electron densities, permitting the evaluation of those energetic properties from the modelling of the topologic…