A variational method for the calculation of spin-rovibronic energy levels of any triatomic molecule in an electronic triplet state

The triatomic spin-rovibronic variational code RVIB3 has been extended to include the effect of two uncoupled electrons, for both (3)Sigma(-) and (3)Pi (Renner-Teller) electronic states. The spin-orbital-rotational kinetic energy is included in the usual way, via terms (J+L+S). The phenomenological terms AL.S and lambda 2/3(3S(z)(2)) are introduced to reproduce the 3 spin-orbit and spin-spin splittings, respectively. Calculations are performed to evaluate the spin-rovibronic energy levels of CCO (X) over tilde (3) Sigma(-) and CCO (A) over tilde (3) Pi for which the Born-Oppenheimer potentials are derived from high-accuracy ab initio calculations.

WRITING ELECTRONIC FERROMAGNETIC STATES IN A HIGH-TEMPERATURE PARAMAGNETIC NUCLEAR SPIN SYSTEM

In this paper, we use Nuclear Magnetic Resonance (NMR) to write electronic states of a ferromagnetic system into high-temperature paramagnetic nuclear spins. Through the control of phase and duration of radio frequency pulses, we set the NMR density matrix populations, and apply the technique of quantum state tomography to experimentally obtain the matrix elements of the system, from which we calculate the temperature dependence of magnetization for different magnetic fields. The effects of the variation of temperature and magnetic field over the populations can be mapped in the angles of spin rotations, carried out by the RF pulses. The experimental results are compared to the Brillouin functions of ferromagnetic ordered systems in the mean field approximation for two cases: the mean field is given by (i) B = B(0) + lambda M and (ii) B = B(0) + lambda M + lambda`M(3), where B(0) is the external magnetic field, and lambda, lambda` are mean field parameters. The first case exhibits second order transition, whereas the second case has first order transition with temperature hysteresis. The NMR simulations are in good agreement with the magnetic predictions.

Electronic structure and chemical bonding in W(2) molecule

The electronic structure of the lowest-lying electronic states of W(2) were investigated at the CASPT2 level. The ground state is a X(1)Sigma(+)(g) state, followed by the a(3)Delta(u), b(3)Sigma(+)(u) and A(1)Delta(u) electronic states. Seven low-lying Omega-states were computed: (1)0(g)(+), (2)3(u), (3)2(u), (4)1(u), (5)0(u)(-), (6)1(u), and (7)2(u), with the ground state corresponding to the (1)0(g)(+)(X(1)Sigma(+)(g)) state. Comparison with the other VIB transition metal group dimers indicates a common pattern of electronic structure and spectroscopic properties. (C) 2010 Elsevier B.V. All rights reserved.

Excited states of the CaAl molecule: An MRCI study

Accurate potential energy curves, dissociation energies and spectroscopic constants for several low-lying doublet and quartet electronic states of CaAl were investigated using the CASSCF/MRCI methodology, and the cc-pVQZ basis set. Our results represent an improvement over a previous theoretical description, and also characterizes new higher excited states not previously investigated, thus confirming the assignment of four excited states investigated experimentally. With the theoretical transition moment functions, transition probabilities and radiative lifetimes were estimated via Einstein spontaneous emission coefficients. (c) 2008 Elsevier B. V. All rights reserved.

A theoretical study of the binding and electronic spectrum of the Mo-2 molecule

Multiconfigurational SCF and second-order perturbation theory have been employed to study seven low-lying singlet and triplet electronic states of the Mo-2 molecule. The bond order of the ground state has been analyzed based on the effective bond order (EBO), indicating that a fully developed sextuple bond is formed between the two Mo atoms. The experimentally observed excited states a(3)Sigma(+)(u) and A(1)Sigma(+)(u) have been determined and the so-called (3)Lambda excited state identified as the b(3)Sigma(+)(u) state, in agreement with experimental expectations. (C) 2007 Elsevier B.V. All rights reserved.

Theoretical study on the molecular mechanism for the reaction of VO2+ with C2H4

The complex reaction between VO2+ ((1)A(1)/(3)A) and C2H4 (Ag-1(g)/(3)A(1)) to yield VO+ ((1)Delta/(3)Sigma) and CH3CHO ('A'/(3)A) has been studied by means of B3LYP/6-31G* and B3LYP/6-311G(2d,p) calculations. The structures of all reactants, products, intermediates, and transition structures of this reaction have been optimized and characterized at the fundamental singlet and first excited triplet electronic states. Crossing points are localized, and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach. Relevant stationary points along the most favorable reaction pathways have been studied at the CCSD/6-311G(2d,p)//B3LYP/6-311G(2d,p) calculation level. The theoretical results allow the development of thermodynamic and kinetic arguments about the reaction pathways of the title process. In the singlet state, the first step is the barrierless obtention of a reactant complex associated with the formation of a V-C bond, while in the triplet state a three-membered ring addition complex with the V bonded to the two C atoms is obtained. Similar behavior is found in the exit channels: the product complexes can be formed from isolated products without barriers. The reactant and product complexes are the most stable stationary points in the singlet and triplet electronic states. From the singlet state reactant complex, two reaction pathways are posssible to reach the triplet state product complex. (i) A mechanism in which a hydrogen transfer process is the first and rate limiting step and the second step is an oxygen transfer between vanadium and carbon atoms with a concomitant change in the spin state. The crossing point between singlet and triplet spin states is not kinetically relevant because it takes place at a later stage occurring in the exit channel. (ii) A mechanism in which the first stage renders a four-membered ring between vanadyl cation and the ethylene fragment and an oxygencarbon bond is formed; on going from this minimum to the second transition structure, associated with a carbon-vanadium bond breaking process, the crossing point between singlet and triplet spin states is reached. The final step is the hydrogen transfer between both carbon atoms to yield the product complex. In this case the spin change opens a lower barrier pathway. The transition structures with larger values of relative energies for both reactive channels of VO2+ ((1)A(1)) + C2H4 (Ag-1) --> VO+ ((3)Sigma) + CH3CHO ((1)A') present similar energies, and the two reaction pathways can be considered as competitive.

Structural, electronic and optical properties of Fe(III) complex with pyridine-2,6-dicarboxylic acid: A combined experimental and theoretical study

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A joint experimental and theoretical study on the electronic structure and photoluminescence properties of Al-2(WO4)(3) powders

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The search for a potentially new molecular species, SiAs: A theoretical contribution

Electronic states of a new molecular species, SiAs, correlating with the three lowest dissociation channels are characterized at a high-level of theory using the CASSCF/MRCI approach along with quintuple-xi quality basis sets. This characterization includes potential energy curves, vibrational energy levels, spectroscopic parameters, dipole and transition dipole moment functions, transition probabilities, and radiative lifetimes. For the ground state (X-2 Pi), an assessment of spin-orbit effects and the interaction with the close-lying A(2)Sigma(+) state is also reported. Similarities and differences with other isovalent species such as SiP and CAs are also discussed.

A theoretical contribution characterizing a potentially new molecular species: MgAs

A new molecular species, MgAs, is investigated theoretically for the first time at the CASSCF/MRCI level using quintuple-zeta quality basis sets. Potential energy curves for the lowest-lying electronic states are presented as well as the associated spectroscopic constants. Dipole and transition moment functions for selected states complement this characterization. Estimates of transition probabilities and radiative life-times for the most important transitions are also reported. The effect of spin-orbit interactions is clearly reflected on the potential energy curves. Comparisons with BeAs, BeN, and BeP are made where pertinent. (C) 2011 Elsevier B.V. All rights reserved.

Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects

The photophysics of the 1-nitronaphthalene molecular system, after the absorption transition to the first singlet excited state, is theoretically studied for investigating the ultrafast multiplicity change to the triplet manifold. The consecutive transient absorption spectra experimentally observed in this molecular system are also studied. To identify the electronic states involved in the nonradiative decay, the minimum energy path of the first singlet excited state is obtained using the complete active space self-consistent field//configurational second-order perturbation approach. A near degeneracy region was found between the first singlet and the second triplet excited states with large spin-orbit coupling between them. The intersystem crossing rate was also evaluated. To support the proposed deactivation model the transient absorption spectra observed in the experiments were also considered. For this, computer simulations using sequential quantum mechanic-molecular mechanic methodology was used to consider the solvent effect in the ground and excited states for proper comparison with the experimental results. The absorption transitions from the second triplet excited state in the relaxed geometry permit to describe the transient absorption band experimentally observed around 200 fs after the absorption transition. This indicates that the T-2 electronic state is populated through the intersystem crossing presented here. The two transient absorption bands experimentally observed between 2 and 45 ps after the absorption transition are described here as the T-1 -> T-3 and T-1 -> T-5 transitions, supporting that the intermediate triplet state (T-2) decays by internal conversion to T-1. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4738757]

Intermolecular and Intramolecular Charge Transfer in Functional Molecular Materials

This thesis is devoted to the investigation of inter and intramolecular charge transfer (CT) in molecular functional materials and specifically organic dyes and CT crystals. An integrated approach encompassing quantum-chemical calculations, semiempirical tools, theoretical models and spectroscopic measurements is applied to understand structure-property relationships governing the low-energy physics of these materials. Four main topics were addressed: 1) Spectral properties of organic dyes. Charge-transfer dyes are constituted by electron donor (D) and electron acceptor (A) units linked through bridge(s) to form molecules with different symmetry and dimensionality. Their low-energy physics is governed by the charge resonance between D and A groups and is effectively described by a family of parametric Hamiltonians known as essential-state models. These models account for few electronic states, corresponding to the main resonance structures of the relevant dye, leading to a simple picture that is completed introducing the coupling of the electronic system to molecular vibrations, treated in a non-adiabatic way, and an effective classical coordinate, describing polar solvation. In this work a specific essential-state model was proposed and parametrized for the dye Brilliant Green. The central issue in this work has been the definition of the diabatic states, a not trivial task for a multi-branched chromophore. In a second effort, we have used essential-state models for the description of the early-stage dynamics of excited states after ultrafast excitation. Crucial to this work is the fully non-adiabatic treatment of the coupled electronic and vibrational motion, allowing for a reliable description of the dynamics of systems showing a multistable, broken-symmetry excited state. 2) Mixed-stack CT salts. Mixed-stack (MS) CT crystals are an interesting class of multifunctional molecular materials, where D and A molecules arrange themselves to form stacks, leading to delocalized electrons in one dimension. The interplay between the intermolecular CT, electrostatic interactions, lattice phonons and molecular vibrations leads to intriguing physical properties that include (photoinduced) phase transitions, multistability, antiferromagnetism, ferroelectricity and potential multiferroicity. The standard microscopic model to describe this family of materials is the Modified Hubbard model accounting for electron-phonon coupling (Peierls coupling), electron-molecular vibrations coupling (Holstein coupling) and electrostatic interactions. We adopt and validate a method, based on DFT calculations on dimeric DA structures, to extract relevant model parameters. The approach offers a powerful tool to shed light on the complex physics of MS-CT salts. 3) Charge transfer in organic radical dipolar dyes. In collaboration with the group of Prof. Jaume Veciana (ICMAB- Barcellona), we have studied spectral properties of a special class of CT dyes with D-bridge-A structure where the acceptor group is a stable radical (of the perchlorotriphenylmethyl, PTM, family), leading to an open-shell CT dyes. These materials are of interest since they associate the electronic and optical properties of CT dyes with magnetic properties from the unpaired electron. The first effort was devoted to the parametrization of the relevant essential-state model. Two strategies were adopted, one based on the calculation of the low-energy spectral properties, the other based on the variation of ground state properties with an applied electric field. 4) The spectral properties of organic nanoparticles based on radical species are investigated in collaboration with Dr. I. Ratera (ICMAB- Barcellona). Intriguing spectroscopic behavior was observed pointing to the presence of excimer states. In an attempt to rationalize these findings, extensive calculations (TD-DFT and ZINDO) were performed. The results for the isolated dyes are validated against experimental spectra in solution. To address intermolecular interactions we studied dimeric structures in the gas phase, but the preliminary results obtained do not support excimer formation.

Spectroscopy and metastability of CO 2 2+ molecular ions

The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO ₂ ²⁺ dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340±0.010 eV. The fragmentation of energy selected CO ₂ ²⁺ ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from ∼38.7 to ∼41 eV above the ground state of neutral CO ₂ has been observed in the experimental time window of ∼0.1-2.3 μs with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO ⁺+O ⁺ formation in indirect dissociative double photoionization below the threshold for formation of CO ₂ ²⁺. The threshold for CO ⁺+O ⁺ formation is found to be 35.56±0.10 eV or lower, which is more than 2 eV lower than previous measurements.

A theoretical study of C4B isomers. The interconversion of CCBCC and CCCCB via cyclic C4B

Theory suggests that CCBCC (1) will rearrange to planar cyclo-C4B (19) if the excess energy of 1 is greater than or equal to16.1 kcal mol(-1) [calculations at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-31G(d) level of theory]. Cyclo-C4B lies only 1.1 kcal mol(-1) above CCBCC. The planar nature of symmetrical cyclo-C4B is attributed to multicentered bonding involving boron. If cyclo-C4B (19) has an excess energy of greater than or equal to24.4 kcal mol-1, it may ring open to form CCCCB (3).

Long-range Coulomb interactions and nanoscale electronic inhomogeneities in correlated oxides

Electronic, magnetic, or structural inhomogeneities ranging in size from nanoscopic to mesoscopic scales seem endemic and are possibly generic to colossal magnetoresistance manganites and other transition metal oxides. They are hence of great current interest and understanding them is of fundamental importance. We show here that an extension, to include long-range Coulomb interactions, of a quantum two-fluid l-b model proposed recently for manganites [Phys. Rev. Lett. 92, 157203 (2004)] leads to an excellent description of such inhomogeneities. In the l-b model two very different kinds of electronic states, one localized and polaronic (l) and the other extended or broad band (b) coexist. For model parameters appropriate to manganites and even within a simple dynamical mean-field theory (DMFT) framework, it describes many of the unusual phenomena seen in manganites, including colossal magnetoresistance (CMR), qualitatively and quantitatively. However, in the absence of long-ranged Coulomb interaction, a system described by such a model would actually phase separate, into macroscopic regions of l and b electrons, respectively. As we show in this paper, in the presence of Coulomb interactions, the macroscopic phase separation gets suppressed and instead nanometer scale regions of polarons interspersed with band electron puddles appear, constituting a kind of quantum Coulomb glass. We characterize the size scales and distribution of the inhomogeneity using computer simulations. For realistic values of the long-range Coulomb interaction parameter V-0, our results for the thresholds for occupancy of the b states are in agreement with, and hence support, the earlier approach mentioned above based on a configuration averaged DMFT treatment which neglects V-0; but the present work has features that cannot be addressed in the DMFT framework. Our work points to an interplay of strong correlations, long-range Coulomb interaction, and dopant ion disorder, all inevitably present in transition metal oxides as the origin of nanoscale inhomogeneities rather than disorder frustrated phase competition as is generally believed. As regards manganites, it argues against explanations for CMR based on disorder frustrated phase separation and for an intrinsic origin of CMR. Based on this, we argue that the observed micrometer (meso) scale inhomogeneities owe their existence to extrinsic causes, e.g., strain due to cracks and defects. We suggest possible experiments to validate our speculation.