Excited-state Spectra Research Articles

Microwave and Quantum Chemical Study of Intramolecular Hydrogen Bonding in 2-Propenylhydrazine (H2C═CHCH2NHNH2).

The microwave spectrum of 2-propenylhydrazine (H2C═CHCH2NHNH2) was studied in the 12-61 and 72-123 GHz spectral regions. A variety of intramolecular hydrogen bonds between one or more of the hydrogen atoms of the hydrazino group and the π-electrons are possible for this compound. Assignments of the spectra of four conformers, all of which are stabilized with intramolecular hydrogen bonds are reported. One hydrogen bond exists in two of these conformers, whereas the π-electrons are shared by two hydrogen atoms in the two other rotamers. Vibrationally excited-state spectra were assigned for three of the four conformers. The internal hydrogen bonds are weak, probably in the 3-6 kJ/mol range. A total of about 4400 transitions were assigned for these four forms. The microwave work was guided by quantum chemical calculations at the B3LYP/cc-pVTZ and CCSD/cc-pVTZ levels of theory. These calculations indicated that as many as 18 conformers may exist for 2-propenylhydrazine and 11 of these have either one or two intramolecular hydrogen bonds. The four conformers detected in this work are among the rotamers with the lowest CCSD electronic energies. The CCSD method predicts rotational constants that are very close to the experimental rotational constants. The B3LYP calculations yielded quartic centrifugal distortion constants that deviated considerably from their experimental counterparts in most cases. The calculation of vibration-rotation constants and sextic centrifugal distortion constants by the B3LYP method were generally found to be in poor agreement with the corresponding experimental constants.

Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of bromobenzene and its perdeuterated isotopologue: Assignment of the vibrations of the S(0), S(1), and D(0)(+) states of bromobenzene and the S(0) and D(0)(+) states of iodobenzene.

We report vibrationally resolved spectra of the S1←S0 transition of bromobenzene using resonance-enhanced multiphoton ionization spectroscopy. We study bromobenzene-h5 as well as its perdeuterated isotopologue, bromobenzene-d5. The form of the vibrational modes between the isotopologues and also between the S0 and S1 electronic states is discussed for each species, allowing assignment of the bands to be achieved and the activity between states and isotopologues to be established. Vibrational bands are assigned utilizing quantum chemical calculations, previous experimental results, and isotopic shifts. Previous work and assignments of the S1 spectra are discussed. Additionally, the vibrations in the ground state cation, D0 (+), are considered, since these have also been used by previous workers in assigning the excited neutral state spectra. We also examine the vibrations of iodobenzene in the S0 and D0 (+) states and comment on the previous assignments of these. In summary, we have been able to assign the corresponding vibrations across the whole monohalobenzene series of molecules, in the S0, S1, and D0 (+) states, gaining insight into vibrational activity and vibrational couplings.

On the CFT operator spectrum at large global charge

We calculate the anomalous dimensions of operators with large global charge $J$ in certain strongly coupled conformal field theories in three dimensions, such as the O(2) model and the supersymmetric fixed point with a single chiral superfield and a $W = \Phi^3$ superpotential. Working in a $1/J$ expansion, we find that the large-$J$ sector of both examples is controlled by a conformally invariant effective Lagrangian for a Goldstone boson of the global symmetry. For both these theories, we find that the lowest state with charge $J$ is always a scalar operator whose dimension $\Delta_J$ satisfies the sum rule $ J^2 \Delta_J - \left( \tfrac{J^2}{2} + \tfrac{J}{4} + \tfrac{3}{16} \right) \Delta_{J-1} - \left( \tfrac{J^2}{2} - \tfrac{J}{4} + \tfrac{3}{16} \right) \Delta_{J+1} = 0.035147 $ up to corrections that vanish at large $J$. The spectrum of low-lying excited states is also calculable explcitly: For example, the second-lowest primary operator has spin two and dimension $\Delta\ll J + \sqrt{3}$. In the supersymmetric case, the dimensions of all half-integer-spin operators lie above the dimensions of the integer-spin operators by a gap of order $J^{1/2}$. The propagation speeds of the Goldstone waves and heavy fermions are $\frac{1}{\sqrt{2}}$ and $\pm \frac{1}{2}$ times the speed of light, respectively. These values, including the negative one, are necessary for the consistent realization of the superconformal symmetry at large $J$.

Systematics of ground state multiplets of atomic nuclei in the delta-interaction approach

Pairing forces between nucleons in an atomic nucleus strongly influence its structure. One of the manifestations of pair interaction is the ground state multiplet (GSM) formation in the spectrum of low-lying excited states of even–even nuclei. The value of GSM splitting is determined by the value of pair interaction of nucleons; for each isotope, it can be estimated on the basis of experimental nuclear masses. The quality of this estimate is characterized by the degree of reproduction of GSM levels in the nucleus. The GSM systematics in even–even nuclei with a pair of identical nucleons in addition to the filled nuclear core is considered on the basis of delta interaction.

Alternative method for evaluating the pair energy of nucleons in nuclei

An alternative method for determining the odd–even effect parameter related to special features of the Casimir operator in Wigner’s mass formula for nuclei is proposed. A procedure for calculating this parameter is presented. The proposed method relies on a geometric interpretation of the Casimir operator, experimental data concerning the contribution of spin–orbit interaction to the nuclear mass for even–even and odd–odd nuclei, and systematics of energy gaps in the spectra of excited states of even–even nuclei.

Theoretical Study of Graphene Nanoflakes with Nitrogen and Vacancy Defects: Effects of Flake Sizes and Defect Types on Electronic Excitation Properties

We have established finite-sized model molecules of hexagonal graphene nanoflakes which consisted of up to about 400 carbon atoms and certain defects and calculated their geometric structures, molecular orbitals, and valence electron excitation properties by DFT and TD-DFT approaches. Several types of defects such as single nitrogen atom dopants, vacancies, combinations of nitrogen atoms and vacancies, etc. have been investigated. The vertical excitation energies and the corresponding absorption spectra of all low-lying excited states of all these defects are found strongly depending on nanoflake sizes with few exceptions. The reason is revealed by examining molecular orbital configuration changes upon excitation, where in most cases the electron density does not localize in the defect center but disperses to the edges of the nanoflake instead. As a result, graphene nanoflakes with these defects do not present definite spectral features like a zero-phonon line in the nanodiamond. The energy gaps and absorption spectra could be tuned by varying nanoflake sizes and defect types, where the size determines the positions of the first major absorption peaks and the defect type affects spectral shapes of the following bands.

Excited-state quantum phase transitions in finite many-body systems

Quantum spectra of excited states of numerous collective many-body models show singularities related to stable and unstable stationary points of the corresponding classical dynamics. We show several examples of these singularities and discuss some of their consequences.

Metal-Enhanced Fluorescence: Wavelength-Dependent Ultrafast Energy Transfer

The fluorescence of dye molecules often shows a strong increase in intensity near metal surfaces or nanoparticles. The excited-state dynamics of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) in the presence of a silver island film (SIF) were explored by femtosecond transient absorption spectroscopy. Under 403 nm excitation, we found clear differences in the excited-state spectra and kinetics of DCM with the SIF. From the analysis of the emission kinetics of DCM, an additional process with a 40–60 ps time constant was distinguished, which was hypothesized to be surface plasmon-coupled fluorescence. This ultrafast process for 403 nm excitation was confirmed as ultrafast energy transfer directly from the surface plasmon of the SIF to DCM. Under 480 nm excitation, no such ultrafast process was observed, but a constant increase in the emission intensity by ∼10% due to the increased electric field of the silver nanoparticles occurred.

Assignment of the vibrations of the S, S1, and D+ states of perhydrogenated and perdeuterated isotopologues of chlorobenzene

We report vibrationally resolved spectra of the S1←S0 transition of chlorobenzene using resonance-enhanced multiphoton ionization spectroscopy. We study chlorobenzene-h5 as well as its perdeuterated isotopologue, chlorobenzene-d5. Changes in the form of the vibrational modes between the isotopologues and also between the S0 and S1 electronic states are discussed for each species. Vibrational bands are assigned utilizing quantum chemical calculations, previous experimental results, and isotopic shifts, including those between the (35)Cl and (37)Cl isotopologues. Previous work and assignments of the S1 spectra are discussed. Additionally, the vibrations in the ground state cation, D0 (+), are considered, since these have also been used by previous workers in assigning the excited neutral state spectra.

Excited State Absorption from Real-Time Time-Dependent Density Functional Theory

The optical response of excited states is a key property used to probe photophysical and photochemical dynamics. Additionally, materials with a large nonlinear absorption cross-section caused by two-photon (TPA) and excited state absorption (ESA) are desirable for optical limiting applications. The ability to predict the optical response of excited states would help in the interpretation of transient absorption experiments and aid in the search for and design of optical limiting materials. We have developed an approach to obtain excited state absorption spectra by combining real-time (RT) and linear-response (LR) time-dependent density functional theory (TDDFT). Being based on RT-TDDFT, our method is aimed at tackling larger molecular complexes and materials systems where excited state absorption is predominantly seen and many time-resolved experimental efforts are focused. To demonstrate our method, we have calculated the ground and excited state spectra of H₂⁺ and H₂ due to the simplicity in the interpretation of the spectra. We have validated our new approach by comparing our results for butadiene with previously published results based on quadratic response (QR). We also present results for oligofluorenes, where we compare our results with both QR-TDDFT and experimental measurements. Because our method directly measures the response of an excited state, stimulated emission features are also captured; although, these features are underestimated in energy which could be attributed to a change of the reference from the ground to the excited state.

Rigid Coumarins: a Complete DFT, TD-DFT and Non Linear Optical Property Study.

The electronic structures and photophysical properties of rigid coumarin dyes have been studied by using quantum chemical methods. The ground-state geometries of these dyes were optimized using the Density Functional Theory (DFT) methods. The lowest singlet excited state was optimized using Time -Dependent Density Functional Theory [TD-B3LYP/6-31G(d)]. On the basis of ground- and excited-state geometries, the absorption and emission spectra have been calculated using the DFT and TD-DFT method. All the calculations were carried out in gas phase and in acetonitrile medium. The results show that the absorption maxima and fluorescence emission maxima calculated using the Time-Dependent Density Functional Theory is in good agreement with the available experimental results. To understand the Non- Linear Optical properties of coumarin dyes we computed dipole moment (μ), electronic polarizability (α), mean first hyperpolarizability (βo) and second hyperpolarizability (γ) using B3LYP density functional theory method in conjunction with 6-31G(d) basis set.

Core-excitation from excited triplet states of organic molecules: X-ray absorption spectra and doubly excited potential curves

SynopsisSoft X-ray absorption spectra of the lowest excited triplet states of several organic molecules (quinones, benzaldehydes, and other carbonyls) and potential curves of valence- and core- doubly excited states are calculated for the O 1s region.

Holographic heavy quark symmetry

We investigate the heavy quark spin symmetry, i.e. the mass degeneracy of pseudo-scalar and vector quarkonia at heavy quark limit, by using the gauge/gravity correspondence. We allow generic D3-like geometry with a flavor D7-brane, to avoid supersymmetric mass degeneracy. For geometries admitting physical QCD-like properties, we find that the mass degeneracy is generically achieved in a good accuracy, up to a few percent mass splitting. We also compute spectra of excited quarkonia states, and discuss comparisons with experiments and quark-model calculations.

Lattice baryon spectroscopy with multiparticle interpolators

In $2+1$ flavor lattice QCD, the spectrum of the nucleon is presented for both parities using local meson-baryon-type interpolating fields in addition to the standard three-quark nucleon interpolators. The role of local five-quark operators in extracting the nucleon excited-state spectrum via correlation matrix techniques is explored on dynamical gauge fields with ${m}_{\ensuremath{\pi}}=293\text{ }\text{ }\mathrm{MeV}$, leading to the observation of a state in the region of the noninteracting S-wave $N\ensuremath{\pi}$ scattering threshold in the negative-parity sector. Furthermore, the robustness of the variational technique is examined by studying the spectrum on a variety of operator bases. Fitting a single-state ansatz to the eigenstate-projected correlators provides robust energies for the low-lying spectrum that are essentially invariant despite being extracted from qualitatively different bases.

Spectroscopy of doubly charmed baryons from lattice QCD

We present the ground and excited state spectra of doubly charmed baryons from lattice QCD with dynamical quark fields. Calculations are performed on anisotropic lattices of size $1{6}^{3}\ifmmode\times\else\texttimes\fi{}128$, with inverse spacing in temporal direction ${a}_{t}^{\ensuremath{-}1}=5.67(4)\text{ }\mathrm{GeV}$ and with a pion mass of about 390 MeV. A large set of baryonic operators that respect the symmetries of the lattice yet which retain a memory of their continuum analogues are used. These operators transform as irreducible representations of ${\mathrm{SU}(3)}_{F}$ symmetry for flavor, SU(4) symmetry for Dirac spins of quarks and O(3) for spatial symmetry. The distillation method is utilized to generate baryon correlation functions which are analyzed using the variational fitting method to extract excited states. The lattice spectra obtained have baryonic states with well-defined total spins up to $7/2$ and the pattern of low-lying states does not support the diquark picture for doubly charmed baryons. On the contrary the calculated spectra are remarkably similar to the expectations from models with an $\mathrm{SU}(6)\ifmmode\times\else\texttimes\fi{}\mathrm{O}(3)$ symmetry. Various spin-dependent energy splittings between the extracted states are also evaluated.

Identification of the Excited-State C═C and C═O Modes of trans-β-Apo-8'-carotenal with Transient 2D-IR-EXSY and Femtosecond Stimulated Raman Spectroscopy.

Assigning the vibrational modes of molecules in the electronic excited state is often a difficult task. Here we show that combining two nonlinear spectroscopic techniques, transient 2D exchange infrared spectroscopy (T2D-IR-EXSY) and femtosecond stimulated Raman spectroscopy (FSRS), the contribution of the C═C and C═O modes in the excited-state vibrational spectra of trans-β-apo-8'-carotenal can be unambiguously identified. The experimental results reported in this work confirm a previously proposed assignment based on quantum-chemical calculations and further strengthen the role of an excited state with charge-transfer character in the relaxation pathway of carbonyl carotenoids. On a more general ground, our results highlight the potentiality of nonlinear spectroscopic methods based on the combined use of visible and infrared pulses to correlate structural and electronic changes in photoexcited molecules.

Rotation-vibration interactions in the spectra of polycyclic aromatic hydrocarbons: Quinoline as a test-case species.

Polycyclic aromatic hydrocarbons (PAHs) are highly relevant for astrophysics as possible, though controversial, carriers of the unidentified infrared emission bands that are observed in a number of different astronomical objects. In support of radio-astronomical observations, high resolution laboratory spectroscopy has already provided the rotational spectra in the vibrational ground state of several molecules of this type, although the rotational study of their dense infrared (IR) bands has only recently become possible using a limited number of experimental set-ups. To date, all of the rotationally resolved data have concerned unperturbed spectra. We presently report the results of a high resolution study of the three lowest vibrational states of quinoline C9H7N, an N-bearing naphthalene derivative. While the pure rotational ground state spectrum of quinoline is unperturbed, severe complications appear in the spectra of the ν45 and ν44 vibrational modes (located at about 168 cm(-1) and 178 cm(-1), respectively). In order to study these effects in detail, we employed three different and complementary experimental techniques: Fourier-transform microwave spectroscopy, millimeter-wave spectroscopy, and Fourier-transform far-infrared spectroscopy with a synchrotron radiation source. Due to the high density of states in the IR spectra of molecules as large as PAHs, perturbations in the rotational spectra of excited states should be ubiquitous. Our study identifies for the first time this effect and provides some insights into an appropriate treatment of such perturbations.

Resonances in coupledπK,ηKscattering from lattice QCD

Coupled-channel $\pi K$ and $\eta K$ scattering amplitudes are determined by studying the finite-volume energy spectra obtained from dynamical lattice QCD calculations. Using a large basis of interpolating operators, including both those resembling a $q\bar{q}$ construction and those resembling a pair of mesons with relative momentum, a reliable excited-state spectrum can be obtained. Working at ${m_\pi=391\,\mathrm{MeV}}$, we find a gradual increase in the $J^P=0^+$ $\pi K$ phase-shift which may be identified with a broad scalar resonance that couples strongly to $\pi K$ and weakly to $\eta K$. The low-energy behavior of this amplitude suggests a virtual bound-state that may be related to the $\kappa$ resonance. A bound state with $J^P=1^-$ is found very close to the $\pi K$ threshold energy, whose coupling to the $\pi K$ channel is compatible with that of the experimental $K^\star(892)$. Evidence is found for a narrow resonance in $J^P=2^+$. Isospin--3/2 $\pi K$ scattering is also studied and non-resonant phase-shifts spanning the whole elastic scattering region are obtained.

Numerical detection of symmetry-enriched topological phases with space-group symmetry

Topologically ordered phases of matter, in particular so-called symmetry enriched topological (SET) phases, can exhibit quantum number fractionalization in the presence of global symmetry. In Z_2 topologically ordered states in two dimensions, fundamental translations T_x and T_y acting on anyons can either commute or anticommute. This property, crystal momentum fractionalization, can be seen in a periodicity of the excited-state spectrum in the Brillouin zone. We present a numerical method to detect the presence of this form of symmetry enrichment given a projected entangled pair state (PEPS); we study the minima of spectrum of correlation lengths of the transfer matrix for a cylinder. As a benchmark, we demonstrate our method using a modified toric code model with perturbation. An enhanced periodicity in momentum clearly reveals the anticommutation relation {T_x,T_y}=0$ for the corresponding quasiparticles in the system.

Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. I. Full cumulant expansions and system-bath entanglement.

We study the Förster resonant energy transfer rate, absorption and emission spectra in multichromophoric systems. The multichromophoric Förster theory (MCFT) is determined from an overlap integral of generalized matrices related to the donor's emission and acceptor's absorption spectra, which are obtained via a full 2nd-order cumulant expansion technique developed in this work. We calculate the spectra and MCFT rate for both localized and delocalized systems, and calibrate the analytical 2nd-order cumulant expansion with the exact stochastic path integral method. We present three essential findings: (i) The role of the initial entanglement between the donor and its bath is found to be crucial in both the emission spectrum and the MCFT rate. (ii) The absorption spectra obtained by the cumulant expansion method are nearly identical to the exact spectra for both localized and delocalized systems, even when the system-bath coupling is far from the perturbative regime. (iii) For the emission spectra, the cumulant expansion can give reliable results for localized systems, but fail to provide reliable spectra of the high-lying excited states of a delocalized system, when the system-bath coupling is large and the thermal energy is small. This paper also provides a simple golden-rule derivation of the MCFT, reviews existing methods, and motivates further developments in the subsequent papers.