1B2 State Research Articles

Interaction-driven first-order and higher-order topological superconductivity

We investigate topological superconductivity in the Rashba-Hubbard model, describing heavy-atom superlattice and van der Waals materials with broken inversion. We focus in particular on fillings close to the van Hove singularities, where a large density of states enhances the superconducting transition temperature. To determine the topology of the superconducting gaps and to analyze the stability of their surface states in the presence of disorder and residual interactions, we employ an fRG+MFT approach, which combines the unbiased functional renormalization group (fRG) with a real-space mean-field theory (MFT). Our approach uncovers a cascade of topological superconducting states, including A1 and B1 pairings, whose wave functions are of dominant p- and d-wave character, respectively, as well as a time-reversal breaking A1+iB1 pairing. While the A1 and B1 states have first-order topology with helical and flat-band Majorana edge states, respectively, the A1+iB1 pairing exhibits second-order topology with Majorana corner modes. We investigate the disorder stability of the bulk superconducting states, analyze interaction-induced instabilities of the edge states, and discuss implications for experimental systems. Published by the American Physical Society 2024

Signatures of Conical Intersections in Extreme Ultraviolet Photoelectron Spectra of Furan Measured with 15 fs Time Resolution.

Ultrafast internal conversion of furan upon deep UV excitation at 200 nm is studied by using extreme ultraviolet time-resolved photoelectron spectroscopy with a time resolution of 15 fs. Ballistic nuclear wavepacket motion from the 1B2(ππ*) state to the ground state is fully observed using 21.7 eV probe pulses. Through the performance of a comparison with the results of electronic structure calculations at the MS(3)-CASPT2(10,10)/cc-pVTZ level of theory, the photoelectron signals from the conical intersection regions are identified.

High-Level Multireference Investigations on the Electronic States in Single-Vacancy (SV) Graphene Defects Using a Pyrene-SV Model.

The nonplanar character of graphene with a single carbon vacancy (SV) defect is investigated utilizing a pyrene-SV model system by way of complete-active-space self-consistent field theory (CASSCF) and multireference configuration interaction singles and doubles (MR-CISD) calculations. Planar structures were optimized with both methods, showing the 3B1 state to be the ground state with three energetically close states within an energy range of 1 eV. These planar structures constitute saddle points. However, following the out-of-plane imaginary frequency yields more stable (by 0.22 to 0.53 eV) but nonplanar structures of Cs symmetry. Of these, the 1A' structure is the lowest in energy and is strongly deformed into an L shape. Following a further out-of-plane imaginary frequency in the nonplanar structures leads to the most stable but most deformed singlet structure of C1 symmetry. In this structure, a bond is formed between the carbon atom with the dangling bond and a carbon of the cyclopentadienyl ring. This bond stabilizes the structure by more than 3 eV compared to the planar 3B1 structure. Higher excited states were calculated at the MR-CISD level, showing a grouping of four states low in energy and higher states starting around 3 eV.

Electronic structure of low-lying states of triatomic MoS2 molecule. The building block of 2D MoS2.

Molybdenum disulfide (MoS2) is the building component of 1D-monolayer, 2D-layered nanosheets and nanotubes having many applications in industry, and it is detected in molecular systems observed in nature. Here, the electronic structure and the chemical bonding of sixteen low-lying states of the triatomic MoS2 molecule are investigated, while the connection of the chemical bonding of the isolated MoS2 molecule to the relevant 2D-MoS2, is emphasized. The MoS2 molecule is studied via DFT and multireference methodologies, i.e., MRCISD(+Q)/aug-cc-pVQZ(-PP)Mo. The ground state, 3B1, is bent (Mo-S=2.133 Å and φ(SMoS)=115.9°) with a dissociation energy to atomic products of 194.7 kcal/mol at MRCISD+Q. In the ground and in the first excited state a double bond is formed between Mo and each S atom, i.e., . These two states differ in which d electrons of Mo are unpaired. The Mo-S bond distances of the calculated states range from 2.108-2.505 Å, the SMoS angles range from 104.1-180.0°, and the Mo-S bonds are single or double. Potential energy curves and surfaces have been plotted for the 3B1, 5A1 and 5B1 states. Finally, the low-lying septet states of the triatomic molecule are involved in the material as a building block, explaining the variety of its morphologies.

An investigating on the structures of Sc2Ge6− cluster and its CO adsorption by quantum chemical calculation

AbstractThe structures of the Sc2Ge6− cluster and its CO adsorption have been computational investigated. The density functional theory and couple cluster calculation are used to gether with the genetic algorithm in determine the minimum structures. This global minimum structure has the shape of a tetragonal bipyramid having two Sc atoms at two tops of pyramids binding with one edge of Ge‐Ge. The ground electronic state of the global minimum isomer is the 2B2 state in the C2v symmetry. The most stable isomer of Sc2Ge6− has been used to study the CO adsorption. The calculated results indicate that the Sc2Ge6− cluster has a good interaction with the CO molecule. The adsorption positions are around the Sc atom with two stable models include adsorbing the C atom and adsorbing both the C and O atoms of the CO molecule. Scandium doped germanium cluster can be used to produce materials that can treat CO gas by adsorption method.

Electron Detachments of NbSin–/0 (n = 1–3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations

The electronic states of NbSin-/0/+ (n = 1-3) clusters have been explored using the state-of-the-art DMRG-CASPT2 method with relatively large active spaces. The leading configurations, bond distances, vibrational frequencies, and relative energies of the low-lying states were identified. Electron detachment energies of the anionic cluster and ionization energies of the neutral clusters were reported at the DMRG-CASPT2 level. The ground states of the NbSin-/0/+ (n = 1-3) clusters were predicted as the 3Δ, 4Π, and 5Π states of the linear NbSi-/0/+, the 3A2, 4B1, and 3B1 states of cyclic NbSi2-/0/+, and the 1A', 2A', and 3A″ states of tetrahedral NbSi3-/0/+ isomers. The first feature in the photoelectron spectrum of NbSi- was attributed to the transitions from the anionic 3Δ ground state to the neutral 4Π, 4Δ, and 4Φ states, whereas the second feature was assigned to the transitions to the neutral 2Δ, 2Σ+, and 2Φ states. The first band in the photoelectron spectrum of NbSi3- was ascribed to the transition from the anionic 1A' ground state to the neutral 12A' and 12A″ states; the second band was attributed to the transitions to 22A', 22A″, and 32A' states; and the third band was assigned to the transition to 32A' states.

Non-adiabatic coupling in the potential energy surfaces of SO2 molecule.

To investigate the potential energy surfaces and the coupling between the adiabatic states of SO2 molecules, it is necessary to consider the non-adiabatic coupling terms (NACTs), where the Born-Oppenheimer approximation breaks down. In this work, we analyze the conical intersections between 1 1A1 and 1 1B2 states (the A' states in Cs symmetry) and 1 1A2 and 1 1B1 states (the A'' states in Cs symmetry) using NACTs and adiabatic-to-diabatic transformation (ADT) angles. Our results confirm reasonable interaction between 1 1A1 and 1 1B2 states and strong interaction between 1 1A2 and 1 1B1 states.

CHANGES IN THE STRUCTURAL-PHASE STATE AND DISLOCATION DENSITY OF TI49.8NI502 ALLOY DEPENDING ON THE ISOCHRONOUS ANNEALING TEMPERATURE AFTER SEVERE PLASTIC DEFORMATION BY ABC PRESSING AT 573 K

X-ray diffraction studies were conducted to examine changes in the structural-phase state and dislocation density of Ti498Ni50.2 alloy depending on the isochronous annealing temperature after severe plastic deformation by abc pressing at 573 K. The total true strain achieved in the alloy samples during abc pressing was e = 9.55. Isochronous annealing was carried out for 1 hour at 573, 673, 773, 873 and 973 K. Room-temperature analysis of all studied samples revealed the coexistence of R and B19' phases, whose relative fractions varied with annealing temperature. The high-temperature B2 phase was not detected. It was found that the most rapid decrease in the dislocation density, which was measured at 393 K (in the B2 state), occurs after annealing the samples at 673 and 773 K. After annealing at 773 K, the dislocation density reaches a minimum, and its value decreases by more than an order of magnitude compared to the value immediately after abc pressing. In the same temperature range there is a significant decrease in the root-mean-square B2 lattice microdistortions (e2)1/2 and a slight increase in the average size of coherent scattering regions. After abc pressing and after isochronous annealing, the main contribution to the physical peak broadening is made by the B2 lattice microdistortions, while the contribution from coherent scattering regions is insignificant. The obtained results show that intense recrystallization in Ti49 8Ni50.2 alloy after abc pressing at 573 K begins at T > 773 K.

Estimation of Excited-State Geometries of Benzene and Fluorobenzene through Vibronic Analyses of Absorption Spectra

The parameters used in theoretical modeling of vibrational patterns within Franck–Condon (FC) approximation can be adjusted to match the vibrationally well-resolved experimental absorption spectrum of molecules. These simulation parameters can then be used to reveal the structural changes occurring between the initial and final states assuming the harmonic oscillator approximation holds for both states. Such a theoretical approach has been applied to benzene and fluorobenzene to disclose the first excited-state geometries of both compounds. The carbon–carbon bond length of benzene in the 1B2u state has been calculated as 1.430 Å, which is in very good agreement with the experimental bond length of 1.432 Å. The FC spectral fit method has been exploited to reveal the 1B2 state of fluorobenzene as well. Commonly employed density functional theory (DFT) and time-dependent DFT methods have been used to calculate the ground- and excited-state geometries of both compounds, respectively. The comparison of geometrical parameters and vibrational frequencies at the relevant states shows that frequently used hybrid functionals perform quite well in the ground state, whereas their performances drop considerably while predicting the excited-state properties. Among the hybrid functionals studied, TD-B3LYP with 6-31+G(d) basis set can be chosen to calculate the excited-state properties of molecules, albeit with much less anticipation of accuracy from the performance that B3LYP usually shows at the ground state.

Measurement of Donor-Acceptor Interchange Tunnelling in Ar(H2O)2 using Rotational Spectroscopy and a Re-look at Its Structure and Bonding

In this work, we have measured the donor-acceptor interchange tunnelling splitting in the ground vibrational state of Ar(H2O)2. In the previous investigations, the donor-acceptor tunnelling splitting in fully deuterated species, Ar(D2O)2, was measured to be about 106 MHz. It could not be measured for Ar(H2O)2, as the splitting was expected to be several GHz. Besides, for (D2O)2, both A1 and B1 states have non-zero statistical weight appearing on both sides of the E1 state, having a semi-rigid rotor type spectrum making their observation easier, compared to that of (H2O)2, which has zero statistical weight for the B1 state. With the help of a fourfold periodic potential, we have accurately predicted the fingerprints of b-dipole A1+↔A1- transitions and observed them using a pulsed nozzle Fourier transform microwave spectrometer. Measurement of these transitions enabled us to determine the donor-acceptor tunnelling splitting of 4257.41(4) MHz in Ar(H2O)2. More detailed structural parameters of Ar(H2O)2 have been evaluated in this work and critically compared with (H2O)2. Atoms in Molecules (AIM), non-covalent interactions (NCI) index and natural bond orbital (NBO) analysis have also been carried out for both (H2O)2 and Ar(H2O)2, and these calculations confirm that the presence of argon (Ar) does not affect the structure and bonding in (H2O)2.

Theoretical Calculations of the 242 nm Absorption of Propargyl Radical.

The propargyl radical, the most stable isomer of neutral C3H3, is important in combustion reactions, and a number of spectroscopic and reaction dynamics studies have been performed over the years. However, theoretical calculations have never been able to find a state that can generate strong absorption around 242 nm as seen in experiments. In this study, we calculated the low-lying electronic energy levels of the propargyl radical using the highly accurate multireference configuration interaction singles and doubles method with triples and quadruples treated perturbatively [denoted as MRCISD(TQ)]. Calculations indicate that this absorption can be attributed to a Franck-Condon-allowed electronic transition from the ground 2B1 state to the Rydberg-like excited state 12A1. Further insight into the behavior of the multireference perturbative theory methods, GVVPT2 and GVVPT3, on a very challenging system are also obtained.

Stationary Points on Potential Energy Surface of Cyclic C3H3 with Coupled-Cluster Approaches and Density Functional Theory.

Cyclic C3H3 is the simplest cyclic hydrocarbon, but its configuration is complicated. The ground 2E″ state at the equilateral triangle geometry with D3h symmetry undergoes both Jahn-Teller (JT) distortion and pseudo-Jahn-Teller (PJT) distortion to structures with C3v, C2v, Cs, or C2 symmetry. Previous works using complete active space self-consistent field (CASSCF) or multiconfiguration SCF (MCSCF) differ on the characteristics of these structures. To clarify the characteristics of these stationary points on the potential energy surface (PES) of this radical, coupled-cluster methods CCSD, CCSD(T), and EOMEA/IP-CCSD as well as density functional theory are employed to calculate their geometries, harmonic frequencies, and relative energies. Deformations between these stationary points due to JT and PJT effects are analyzed in detail. Most of the results with these methods are consistent with each other, except for the b2 mode of the 2B1 state with C2v symmetry. CCSD and CCSD(T) provide an imaginary frequency for this vibrational mode, while it is calculated to be real with the other methods as well as with EOM-CCSDT-3. This may be related to unstable reference in CCSD and CCSD(T) calculations. On the other hand, most of the employed exchange-correlation functionals provide reliable results on the characteristics of these stationary points. Our results show that the 2A' state with Cs symmetry is the only minimum structure on the PES of cyclic C3H3. The 2A2 and 2B1 states of the C2v structure are second-order saddle points, while both the 2A state of the C2 structure and the 2A″ state of the Cs structure are transition states connecting the global minimum 2A' state.

Behavior of Inelastic and Plastic Strains in Coarse-Grained Ti49.3Ni50.7(at%) Alloy Deformed in B2 States

The regularities of the change in inelastic strain in coarse-grained samples of the Ti49.3Ni50.7 (at%) alloy are studied when the samples are given torsional strain in the state of the high-temperature B2 phase. During cooling and heating, the investigated samples underwent the B2–B19′ martensite transformation (MT); the temperature of the end of the reverse MT was Af = 273 K. It was found that at the temperature of isothermal cycles “loading-unloading” Af + 8 K, when the specimen is assigned a strain of 4%, the effect of superelasticity is observed. With an increase in the torsional strain, the shape memory effect is clearly manifested. It is assumed that the stabilization of the B19′ phase in unloaded samples is due to the appearance of dislocations during deformation due to high internal stresses at the interphase boundaries of the B2 phase and the martensite phase during MT. The appearance of dislocations during the loading of samples near the temperatures of forward and reverse MT can also be facilitated by the “softening” of the elastic moduli of the alloy in this temperature range. At a test temperature above Af + 26 K, the superelasticity effect dominates in the studied samples.

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F2O+ cation within multi reference configuration interaction calculations

AbstractIn F2O+ cation the first (2B2) and second excited (2A1) electronic states can be coupled with each other by anti‐symmetric stretching mode and thus conical intersection and non‐adiabatic dynamics play an important role in characterizing molecular properties. In this work, we tried to find a suitable computational method for determining equilibrium structures and harmonic vibrational frequencies of the three lowest electronic states of F2O+. To understand non‐adiabatic dynamics at conical intersections, we calculated the probability of electronic population on 2B2 and 2A1 excited electronic states using linear vibronic coupling Hamiltonian mode including all three vibrational modes (bending (ω1), symmetric stretching (ω2) and anti‐symmetric stretching (ω3)).The amount of vibronic coupling constant between these states is obtained 0.08 eV at multi reference configuration interaction/Aug‐cc‐pVQZ level of theory.

Photodissociation Dynamics of H2O via the Ẽ' (1B2) Electronic State.

Photodissociation dynamics of H2O via the Ẽ'1B2 state were studied using the high-resolution H atom photofragment translational spectroscopy method, in combination with the tunable vacuum ultraviolet free electron laser (VUV FEL). The measured translational energy spectra allow us to determine the respective quantum state population distributions for the nascent OH(X2Π) and OH(A2Σ+) photofragments. Analyses of the quantum state population distributions show both the ground and electronically excited OH fragments to be formed with moderate vibrational excitation but with highly rotational excitation. Unlike the dissociation via the lower-lying electronic states, where OH(X) is the major fragment, the OH(A) products are predominant via the Ẽ' state. These products are mainly ascribed to a fast dissociation on the B̃1A1 state surface after nonadiabatic transitions from the initial excited Ẽ' state to the B̃ state. Meanwhile, another dissociation pathway from the Ẽ' state to the 1B2 3pb2 state, followed by coupling to the 1A2 3pb2 state, is also observed, which yields the OH(X) + H and O(3P) + 2H products.

Ultrafast Extreme Ultraviolet Photoelectron Spectroscopy of Nonadiabatic Photodissociation of CS2 from 1B2 (1Σu+) State: Product Formation via an Intermediate Electronic State.

We studied nonadiabatic dissociation of CS2 from the 1B2 (1Σu+) state using ultrafast extreme ultraviolet photoelectron spectroscopy. A deep UV (200 nm) laser using the filamentation four-wave mixing method and an extreme UV (21.7 eV) laser using the high-order harmonic generation method were employed to achieve the pump-probe laser cross-correlation time of 48 fs. Spectra measured with a high signal-to-noise ratio revealed clear dynamical features of vibrational wave packet motion in the 1B2 state; its electronic decay to lower electronic state(s) within 630 fs; and dissociation into S(1D2), S(3PJ), and CS fragments within 300 fs. The results suggest that both singlet and triplet dissociation occur via intermediate electronic state(s) produced by electronic relaxation from the 1B2 (1Σu+) state.

Vibronic coupling in the Pyridine Radical Cation: Nuclear Dynamics Studied Using the Multi-configuration Time-Dependent Hartree method

The multi-configuration time-dependent Hartree (MCTDH) method was applied to study nuclear dynamics following transitions to a manifold of vibronically coupled ground 2A1 and excited 2A2 and 2B1 states of the pyridine radical cation (PRC). These states originate from ionization out of the highest occupied orbitals of pyridine, 7a1 (nσ), 1a2 (π), and 2b1 (π), respectively, and give rise to the lowest two photoelectron bands. We focus on various theoretical and computational aspects of the MCTDH method and methodology to calculate the spectrum, taking our study of the vibronically interacting 2A1, 2A2, and 2B1 states of PRC as an example. In particular, the choice of the single-particle functions (SPFs) and schemes to combine vibrational modes are discussed.

Dissociation of High-Lying Electronic States of NO2+ in the 15.5-20 eV Region.

We present a dissociative photoionization study of NO2 in the 15.5-20 eV energy range using synchrotron radiation-based double imaging photoelectron photoion coincidence (i2PEPICO) spectroscopy. The high-lying electronic states of the NO2+ cation, c 3B1, C 1B1, d 3A1, e 3B2, and D 1B2, are prepared in well-resolved vibronic states in order to study their individual dissociation mechanisms. Up to eight dissociation limits of NO2+ are reached, and mass-selected threshold photoelectron spectra (TPES) show that the c 3B1, C 1B1, and d 3A1 states predominantly dissociate into the NO+ + O products, while the e 3B2 and D 1B2 states can undergo fragmentation into both the NO+ + O and the O+ + NO channels, as well as the O2+ + N channel with a small yield. Overall, these product yields are found to be quite sensitive to autoionization processes. Mass-selected high-resolution electron and ion kinetic energy correlation diagrams reveal dissociative mechanisms that possess strong state-specific character.

Direct Observation of the C + S2 Channel in CS2 Photodissociation.

Carbon disulfide (CS2) is a typical triatomic molecule. Its photodissociation process has generally been assumed to proceed to CS and S primary products via single bond fission. However, recent theoretical calculations suggested that an exit channel to produce C + S2 should also be energetically accessible. Here, we report the direct experimental evidence for the C + S2 channel in CS2 photodissociation by using the velocity map ion imaging technique with two-photon UV and one-photon vacuum UV (VUV) excitations. The detection of the C (3P) products illustrates that the ground state and the electronically excited states of S2 coproducts are formed within highly excited vibrational states. The very weak anisotropic distributions indicate relatively slow dissociation processes. The possible dissociation mechanism involves molecular isomerization of CS2 to linear-CSS from the excited 1B2 (21Σ+) state via vibronic coupling with the 1Π state followed by an avoided crossing with the ground state surface. Our results imply that the S2 molecules observed in comets might be primarily formed in CS2 photodissociation.

Valence Bond Alternative Yielding Compact and Accurate Wave Functions for Challenging Excited States. Application to Ozone and Sulfur Dioxide.

A novel state-averaged version of ab initio nonorthogonal valence bond method is described, for the sake of accurate theoretical studies of excited states in the valence bond framework. With respect to standard calculations in the molecular orbital framework, the state-averaged breathing-orbital valence bond (BOVB) method has the advantage to be free from the penalizing constraint for the ground and excited state(s) to share the same unique set of orbitals. The ability of the BOVB method to faithfully describe excited states and to compute accurate transition energies from the ground state is tested on the five lowest-lying singlet electronic states of ozone and sulfur dioxide, among which 11B2 and 21A1 are the challenging ones. As the 11A2, 11B1, and 11B2 states are of different symmetries than the ground state, they can be calculated at the state-specific BOVB level. On the other hand, the 21A1 states and the 11A1 ground states, which are of like symmetry, are calculated with the state-averaged BOVB technique. In all cases, the calculated vertical energies are close to the experimental values when available, and at par with the most sophisticated calculations in the molecular framework, despite the extreme compactness of the BOVB wave functions, made of no more than 5-9 valence bond structures in all cases. The features that allow the combination of compactness and accuracy in challenging cases are analyzed. For the "ionic" 11B2 states, which are the site of important charge fluctuations, it is because of the built-in dynamic correlation inherent to the BOVB method. For the 21A1 ones, this is the fact that these states have the degree of freedom of having different orbitals than the ground states, even though they are of like symmetry and calculated simultaneously using the newly implemented state-average BOVB algorithm. Finally, the description of the excited states in terms of Lewis structures is insightful, rationalizing the fast ring closure for the 21A1 state of ozone and predicting some diradical character in the so-called "ionic" 11B2 states.