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The recent advent of cutting-edge experimental techniques allows for a precise synthesis of subnanometer metal clusters composed of just a few atoms, opening new possibilities for subnanometer science. In this work, via first-principles modeling, we show how the decoration of perfect and reduced TiO2 surfaces with Ag5 atomic clusters enables the stabilization of multiple surface polarons. Moreover, we predict that Ag5 clusters are capable of promoting defect-induced polarons transfer from the subsurface to the surface sites of reduced TiO2 samples. For both planar and pyramidal Ag5 clusters, and considering four different positions of bridging oxygen vacancies, we model up to 14 polaronic structures, leading to 134 polaronic states. About 71% of these configurations encompass coexisting surface polarons. The most stable states are associated with large inter-polaron distances (>7.5 Å on average), not only due to the repulsive interaction between trapped Ti3+ 3d1 electrons, but also due to the interference between their corresponding electronic polarization clouds [P. López-Caballero et al., J. Mater. Chem. A 8, 6842–6853 (2020)]. As a result, the most stable ferromagnetic and anti-ferromagnetic arrangements are energetically quasi-degenerate. However, as the average inter-polarons distance decreases, most (≥70%) of the polaronic configurations become ferromagnetic. The optical excitation of the midgap polaronic states with photon energy at the end of the visible region causes the enlargement of the polaronic wave function over the surface layer. The ability of Ag5 atomic clusters to stabilize multiple surface polarons and extend the optical response of TiO2 surfaces toward the visible region bears importance in improving their (photo-)catalytic properties and illustrates the potential of this new generation of subnanometer-sized materials. [ABSTRACT FROM AUTHOR]

An efficient full-configuration-interaction nuclear orbital treatment has been recently developed as a benchmark quantum-chemistry-like method to calculate ground and excited “solvent” energies and wave functions in small doped ΔEest clusters (N≤4) [M. P. de Lara-Castells, G. Delgado-Barrio, P. Villarreal, and A. O. Mitrushchenkov, J. Chem. Phys. 125, 221101 (2006)]. Additional methodological and computational details of the implementation, which uses an iterative Jacobi–Davidson diagonalization algorithm to properly address the inherent “hard-core” He–He interaction problem, are described here. The convergence of total energies, average pair He–He interaction energies, and relevant one- and two-body properties upon increasing the angular part of the one-particle basis set (expanded in spherical harmonics) has been analyzed, considering Cl2 as the dopant and a semiempirical model (T-shaped) He–Cl2(B) potential. Converged results are used to analyze global energetic and structural aspects as well as the configuration makeup of the wave functions, associated with the ground and low-lying “solvent” excited states. Our study reveals that besides the fermionic nature of 3He atoms, key roles in determining total binding energies and wave-function structures are played by the strong repulsive core of the He–He potential as well as its very weak attractive region, the most stable arrangement somehow departing from the one of N He atoms equally spaced on equatorial “ring” around the dopant. The present results for N=4 fermions indicates the structural “pairing” of two 3He atoms at opposite sides on a broad “belt” around the dopant, executing a sort of asymmetric umbrella motion. This pairing is a compromise between maximizing the 3He–3He and the He-dopant attractions, and suppressing at the same time the “hard-core” repulsion. Although the He–He attractive interaction is rather weak, its contribution to the total energy is found to scale as a power of three and it thus increasingly affects the pair density distributions as the cluster grows in size. [ABSTRACT FROM AUTHOR]

A new embedding method to include local correlation in large systems is proposed. In this method the density of the whole system, calculated via density functional theory approaches, is partitioned in two pieces, one corresponding to the subsystem of interest and the rest to the environment. In the second step, an embedding potential is obtained iteratively using as a driving force the self-repulsion due to the density difference, in a similar form as proposed by Zhao et al. [Phys. Rev. A 50, 2138 (1994)], to obtain the “exact” exchange-correlation functional. Such potential is added to the Fock equation to build the localized molecular orbitals which are further used to include the local electronic correlation in the subsystem of interest. This method is an alternative to the previous DFT-based embedding methods first proposed by Wesolowski and Washell [J. Phys. Chem. 97, 8050 (1993)] and after enhanced by Govind et al. [J. Chem. Phys. 110, 7677 (1999)] and adapted to metal extended systems, which use density functionals to describe the kinetic energy contribution to the embedding potential, whose precise form has been largely treated in the literature and its crucial role is discussed here. The method is applied to hydrogen chains and its van der Waals interaction with H2. The results obtained are in very good agreement with exact calculations performed on the whole system, which demonstrates that the method proposed is a very promising route to introduce correlation in large systems. [ABSTRACT FROM AUTHOR]

Helium clusters doped with diatomic molecules, HeN–BC, have been recently studied by means of a quantum-chemistry-like approach. The model treats He atoms as “electrons” and dopants as “nuclei” in standard electronic structure calculations. Due to the large mass difference between He atoms and electrons, and to the replacement of Coulomb interactions by intermolecular potentials, it is worth assessing up to what extent are the approximations involved in this model, i.e., decoupling of the BC rotation from the He-atom orbital angular momenta and Born–Oppenheimer separation of the BC stretch versus the He motions, accurate enough. These issues have been previously tackled elsewhere for the 4He2–Br2(X) system, which contains a heavy dopant [Roncero et al., Int. J. Quantum Chem. 107, 2756 (2007)]. Here, we consider a similar cluster but with a much lighter dopant such as N2(X). Although the model does not provide the correct energy levels for the cluster, positions and intensities of the main detectable lines of the vibrotational Raman spectrum at low temperature are accurately reproduced. [ABSTRACT FROM AUTHOR]

An efficient full configuration interaction (FCI) treatment, based on the Jacobi-Davidson algorithm, is developed in order to study small doped 3HeN clusters. The state of each He atom in a given cluster is described by a set of wave-functions which by extention of the quantum-chemistry notation are caller here “nuclear orbitals”. The FCI treatment is applied to the calculation of binding energies and helium natural orbitals of 3HeN...Br2(X) complexes. In agreement with our previous calculations using a Hartree-Fock approach [Phys. Rev. Lett. 93, 053401 (2004)], in which the He–He interaction is modified at small distances to account for short-range correlation effects, the lowest-energy states of each multiplet are found to be very close in energy. The natural orbital analysis, in turn, indicates the adequacy of the “nuclear orbital” approach in these systems. [ABSTRACT FROM AUTHOR]

The CO2(010)–O(3P) vibrational energy transfer (VET) efficiency is a key input to aeronomical models of the energy budget of the upper atmospheres of Earth, Venus, and Mars. This work addresses the physical mechanisms responsible for the high efficiency of the VET process at the thermal energies existing in the terrestrial upper atmosphere (150 K≤=T≤=550 K). We present a quantum-mechanical study of the process within a reduced-dimensionality approach. In this model, all the particles remain along a plane and the O(3P) atom collides along the C2v symmetry axis of CO2, which can present bending oscillations around the linear arrangement, while the stretching C–O coordinates are kept fixed at their equilibrium values. Two kinds of scattering calculations are performed on high-quality ab initio potential energy surfaces (PESs). In the first approach, the calculations are carried out separately for each one of the three PESs correlating to O(3P). In the second approach, nonadiabatic effects induced by spin-orbit couplings (SOC) are also accounted for. The results presented here provide an explanation to some of the questions raised by the experiments and aeronomical observations. At thermal energies, nonadiabatic transitions induced by SOC play a key role in causing large VET efficiencies, the process being highly sensitive to the initial fine-structure level of oxygen. At higher energies, the two above-mentioned approaches tend to coincide towards an impulsive Landau-Teller mechanism of the vibrational to translational (V-T) energy transfer. [ABSTRACT FROM AUTHOR]

The aim of this paper is to elucidate the role played by the bosonic/fermionic character of N He atoms solvating a Br2(X) molecule. To this end, an adiabatic model in the molecular stretching coordinate is assumed and the ground energy levels of the complexes are searched by means of Hartree (or Hartree-Fock) Quantum Chemistry calculations for 4He (or 3He) solvent atoms. Simulations of vib-rotational Raman spectra point at the spin multiplicity as the main feature responsible for the drastic difference in the rotational structures of molecules embedded in boson or fermion helium drops as already observed by the experiments of Grebenev et al. [S. Grebenev, J. P. Toennies, and A. F. Vilesov, Science 279 (1998) 2083]. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The interaction of He with Br[sub 2] in electronically excited B [sup 3]Π[sub u] state is investigated using spin-unrestricted single and double coupled-cluster approach with noniterative perturbative treatment of triple excitations. Internal electrons of the Br atom are described by effective core pseudopotentials. The validity of this approach is analyzed by comparing the lowest [sup 2]Σ[sup +] and [sup 2]Π electronic states of the HeBr molecule with those obtained in all electron calculations [J. Chem. Phys. 115, 10438 (2001)]. In this context, we examine the performance of different basis sets and saturation with bond functions. The comparison of theoretical blue-shifts with the experiment provides confidence about the present ab initio calculations. In addition, He–Br results of ab initio calculations at the same level are used to obtain approximate He–Br[sub 2] ([sup 3]Π[sub u]) interactions in the framework of the diatomics-in-molecule first order perturbation theory (IDIM-PT1) [J. Chem. Phys. 104, 9913 (1996)]. Overall, the IDIM-PT1 model results show a good agreement with the ab initio ones, being the main difference the sensitivity to the elongation of the Br–Br bond. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We investigate the UV-induced desorption of O[sub 2] from a reduced TiO[sub 2] rutile surface. The desorption mechanism considered is a direct, optical excitation of the adsorbate-substrate complex. The low-lying excited electronic states of the adsorbate-surface system and the transition dipole moments are calculated with a cluster model. We also estimate the effects of nonadiabatic coupling on the desorption yield. As a consequence of the localized nature of the adsorption process, ground state properties calculated with the cluster model agree well with previous results obtained with a slab model. To reduce the size of the calculation, we use optimal orbitals for each of the interacting electronic states, followed by transformation to biorthonormal orbital sets. Comparison with experimental photodesorption cross-section data shows excellent agreement for photon energies close to the vertical transition energy. At higher energies, we speculate that substrate-mediated electronic excitation mechanisms must be included in the model. [ABSTRACT FROM AUTHOR]

The lowest [sup 2]Σ[sup +] and [sup 2]Π electronic states of the HeBr molecule have been calculated by the ab initio coupled cluster approach in conjunction with a series of increasing size augmented correlation-consistent basis sets of double through quintuple zeta quality. Different extrapolation formulas to the complete basis set limit have been tested by comparing estimated and actual quintuple zeta quality counterpoise corrected interaction energies. Frozen-core approach is checked by performing calculations in which all electrons are correlated. The potential energy surfaces of the HeBr[sub 2] van der Waals complex have been obtained from the HeBr potentials by means of the diatomic-in-molecule approach. Finally, transport, scattering, and spectroscopic properties of HeBr and HeBr[sub 2](B) systems derived from ab initio data for different basis sets are examined. It is shown that their convergence closely follows the convergence of corresponding potential energy surfaces. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Accurate, highly correlated calculations have been carried out for the ground electronic state and for a few of the lower excited electronic states, two of which are discussed in this work, of the trimer ionic helium cluster. Both linear asymmetric and nonlinear, symmetric, and asymmetric, configurations have been considered over a rather broad range of nuclear geometries. The results confirm the experimentally found [Chem. Phys. 102, 2773 (1995)] fragmentation patterns involving He and He+ fragments only and further suggest a range of possible nuclear geometries from which nonadiabatic couplings could also lead to He2+ fragments, albeit with a lower probability than the former channels. [ABSTRACT FROM AUTHOR]

A full quantum study of the fragmentation dynamics for argon trimer ions is carried out using a previously computed potential energy surface (PES). The initial and final internal states which are being considered are the bending–stretching states of the trimer and the rotovibrational states of the residual dimer ion. The treatment employs the helicity decoupling approximation over a broad range of total angular momentum values (J) and analyses the final distribution of rotational–vibrational states as a function of the metastable states of the J values and of the ‘‘tumbling’’ (helicity) quantum number Ω. It is found that at least two different effects, one mainly dynamically related to the centrifugal barrier and another to the orientational nature of the coupling potential field, can be discerned to explain the fragmentation results. [ABSTRACT FROM AUTHOR]

An efficient full configuration-interaction (CI) treatment has been recently developed as a benchmark quantum chemistry (QC) method to study doped 3He N clusters [J Chem Phys 125:221101, 2006]. The method, which uses an iterative Jacobi–Davidson diagonalization algorithm, is applied here to small clusters ( N ≤ 4) containing Cl2 as dopant. [ABSTRACT FROM AUTHOR]

A quantum-chemistry-like methodology developed recently to study molecules solvated in atomic clusters is reviewed, and the results of its application to diatomic molecules immersed in helium clusters are presented and discussed. The methodology is based on treating the atoms of the solvent cluster as the “electrons” and the solvated molecule (“BC”) as a structured “nucleus” of the combined solvent-solute system. The “electron”-“electron” and “electron”-“nucleus” interactions are represented by parametrized two-body and ab initio three-body potentials, respectively. The “intranuclear” (intramolecular) energy is mimicked by a parametrized pair potential energy function. The methodology furnishes the wave functions, and thereby it allows for computation of the infrared or Raman spectra of the solvated molecules. The computed spectra are then compared with the measured ones. In agreement with the experimental observations, the computed spectra of the solvated molecule show considerable differences depending on whether the solvent cluster is comprised of pure bosonic (4He), pure fermionic (3He), or both bosonic and fermionic helium atoms. The differences in the spectra are explained in terms of the differences in the spin-statistics of the solvent clusters. The bosonic vs fermionic nature of the solvent is also reflected in the selection rules. In the case of a polar molecule, the Q-branch of the spectrum is forbidden when the molecule is solvated in a bosonic cluster, and it becomes allowed when the solvent is a fermionic cluster. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [ABSTRACT FROM AUTHOR]

A quantum chemistry-like approach has been recently developed in our group to deal with HeN–BC doped helium clusters, where the BC dopant is a conventional diatomic molecule. The central idea is to consider the He atoms as “electrons” while the B and C atoms play the role of the nuclei in standard electronic structure calculations. The procedure provides energies and wavefunctions allowing to perform spectral simulations and, hence, making feasible to do proper comparisons with current experiments. However, because of the large difference of masses of He and electrons, and also to the replacement of Coulomb potentials by molecular interactions, it is worthy to assess to what extent the approximations involved in this model (decoupling of orbital angular momenta of the He atoms from the BC rotation and adiabatic separation of the BC stretch versus the He motions) lead to accurate results. In this work we address these issues on the 4He2–Br2(X) system, containing a couple of bosonic He atoms for which variational calculations can be performed. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [ABSTRACT FROM AUTHOR]

The quenching of CO2(010) by thermal collisions with ground-state atomic oxygen is a crucial process in determining the cooling rates of the thermospheres of Earth, Venus and Mars and then to predict changes due to the increase of this green-house gas. One of the questions raised by the experiments and aeronomical observations is with regard to the physical origin of the non-Landau-Teller and negligible temperature dependence of the vibrational relaxation rate at the temperatures existing in the thermospheres (150K≤T≥550 K). In this context, we extend our previous work on quantum scattering calculations performed on high-quality ab initio potential energy surfaces (PESs) [M. P. de Lara-Castells, Marta I. Hernández, G. Delgado-Barrio, P. Villarreal, and M. López-Puertas, J. Chem. Phys. 124, 164302 (2006)]. and report translational-energy averaged quenching probabilities for the previously reported C2v PES as well as for additional orientational approaches of the oxygen atom. Our results reveal the spin-orbit couplings to be responsible for the temperature dependence of the quenching rate estimated from the analysis of upper atmospheric data. In addition, we analyse the effect of the PESs' anisotropy on the quenching process. [ABSTRACT FROM AUTHOR]

We present a theoretical analysis of O[sub 2] adsorption on a reduced TiO[sub 2] (110) rutile surface, based on periodic ab initio Hartree–Fock calculations. Three different orientational approaches, three different spin symmetries, and two different adsorption sites are considered. We also consider the possibility that the surface can absorb more than one oxygen molecule. Positions of the surface ions, oxygen ions belonging to the third and fourth layers of the slab, and the bond lengths of the O[sub 2] and O[sub 2]-substrate distances are optimized. Adsorption energies, admolecule-substrate bond lengths, spin densities and Mulliken charges are analyzed. The model is tested by comparing spin densities and relaxation parameters obtained for the reduced TiO[sub 2] (110) system to previous theoretical results. Finally, we discuss the relationship of our results to experimental observations of thermal desorption rates at low temperatures (100–600 K). © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]