The review is devoted to explanation of SERS in terms of the dipole and quadrupole light-molecule interactions arising in surface fields strongly varying in space in the region of the strongly irregular surface roughness. The main SERS characteristics, the theory of electromagnetic fields near some model kinds of rough surfaces and some other systems, the theory of SERS Raman tensor for arbitrary and symmetrical molecules, selection rules and analysis of the SER spectra, some anomalies in the SER spectra of symmetrical molecules for some specific conditions, electrodynamic forbiddance of the quadrupole scattering mechanism for the methane molecule and molecules with cubic symmetry groups are considered. The huge enhancement and blinking of the SERS signal arising in the phenomenon of Single Molecule detection by the SERS method are explained. The above theory is compared with some another SERS mechanisms, and the phenomena accompanying SERS are accounted for. It is demonstrated that the theory is in a good agreement with the experiment and explains quite a number of characteristics related to the SERS phenomenon.
The expression for the SEHR cross-section of symmetrical molecules within the framework of the dipole-quadrupole theory is obtained. It is formed by contributions, which depend on various dipole and quadrupole moments. Estimation of the enhancement coefficients for the quadrupole enhancement mechanism in some limited case can achieve the value . It is demonstrated that the contributions follow some selection rules. Qualitative classification of the contributions after the enhancement degree is given.
The paper analyses the SEHR spectra of symmetrical molecules on the base of the dipole-quadrupole SEHRS theory. Existence of the bands, caused by vibrations transforming after the unit irreducible representations of corresponding symmetry groups is demonstrated. As it follows from the theoretical group analysis, these bands are forbidden in phenazine, pyrazine and in usual HRS in molecules belonging to a large number of groups (Cnh, D and higher symmetry groups for example). Their appearance strongly confirms the dipole-quadrupole SEHRS theory, which is able to explain other features of the SE…
The paper presents main aspects of the Dipole-Quadrupole theory of Surface Enhanced Infrared Absorption (SEIRA). It is pointed out the possibility of appearance of the lines, caused by totally symmetric vibrations transforming after the unit irreducible representation, which are forbidden in usual infrared absorption spectra in molecules with sufficiently high symmetry. Observation of such lines in the SEIRA spectra of diprotonated and ethylene, adsorbed on and on mordenites is pointed out. The results well agree with our ideas about surface enhanced optical processes, based on the conception …
It is demonstrated in the framework of the Dipole-Quadrupole theory, that strong quadrupole light-molecule interaction, which is responsible for the most enhancement of SEHRS in the methane molecule, which belongs to the symmetry group, experiences so-called electrodynamical forbiddance due to electrodynamical law, and does not influence on the formation of the SEHRS spectra. This forbiddance results in the fact that the lines, caused by the totally symmetric vibrations, transforming after the unit irreducible representation, which are observed in symmetrical molecules with another sufficientl…
We have performed Fourier transform microwave spectroscopy of benzonitrile, without and with applied electric fields. From the field-free hyperfine-resolved microwave transitions we simultaneously derive accurate values for the rotational constants, centrifugal distortion constants, and nitrogen nuclear quadrupole coupling constants of benzonitrile. By measuring the Stark shift of selected hyperfine transitions the electric dipole moment of benzonitrile is determined to $μ=μ_a=4.5152 (68)$ D.
The Dipole-Quadrupole theory of Surface Enhanced Hyper Raman Scattering (SEHRS), created by the authors is expounded in details. Peculiarities of the behavior of electromagnetic field on rough metal surfaces are considered. It is demonstrated that there is an enhancement of the dipole and quadrupole light-molecule interaction near the places with a large curvature. The expression for the SEHRS cross-section of symmetrical molecules, which consists of several contributions is obtained. Selection rules for the scattering contributions are obtained and a qualitative classification of the contribu…
Molecular absorption of infrared radiation is generally due to ro-vibrational electric-dipole transitions. Electric-quadrupole transitions may still occur, but they are typically a million times weaker than electric-dipole transitions, rendering their observation extremely challenging. In polyatomic or polar diatomic molecules, ro-vibrational quadrupole transitions have never been observed. Here, we report the first direct detection of quadrupole transitions in water vapor. The detected quadrupole lines have intensity largely above the standard dipole intensity cut-off of spectroscopic databas…
The paper demonstrates possibility of giant enhancement of Surface Enhanced Hyper Raman Scattering on the base of qualitative consideration of electromagnetic field near some models of rough metal surfaces and of some features of the dipole and quadrupole light-molecule interaction, such as it was made in the dipole-quadrupole SERS theory. Consideration of symmetrical molecules allows to obtain selection rules for their SEHR spectra and establish such regularity as appearance of the bands, caused by the totally symmetric vibrations, transforming after the unitary irreducible representation in …
A minimal, one-parameter model of the excitonic Hamiltonian for the light harvesting complex of purple bacteria (LH2) based on ab initio calculation of the excitonic energies is proposed. The set of input parameters contains positions of atoms in 27 bacteriochlorophyll pigments only. The excitation energies, transition dipole and quadrupole moments of the bacteriochlorophyll units were calculated by advanced multiconfigurational multireference method. In the work we investigate influence of the dipole-quadrupole interaction on the particularities of the absorption spectra and circular dichrois…
The paper demonstrates possibility of giant enhancement of Surface Enhanced Hyper Raman Scattering on the base of qualitative consideration of electromagnetic field near some models of rough metal surfaces and of some features of the dipole and quadrupole light-molecule interaction, such as it was made in the dipole-quadrupole SERS theory. Consideration of symmetrical molecules allows to obtain selection rules for their SEHR spectra and establish such regularity as appearance of the lines, caused by totally symmetric vibrations, transforming after the unit irreducible representation in molecul…
We have employed the relativistic coupled cluster theory to calculate the magnetic dipole and electric quadrupole hyperfine constants for the ground and low lying excited states of singly ionized magnesium. Comparison with experimental and the other theoretical results are done and predictions are also made for a few low lying excited states which could be of interest. We have made comparative studies of the important many body effects contributing to the hyperfine constants for the different states of the ion.
For electronic excitations in the ultraviolet and visible range of the electromagnetic spectrum, the intensities are usually calculated within the dipole approximation, which assumes that the oscillating electric field is constant over the whole molecule. For the short wavelengths used in X-ray spectroscopy, this dipole approximation breaks down and it becomes necessary to include higher-order contributions. In quantum-chemical approaches to X-ray spectroscopy, these so-called quadrupole intensities have so far been calculated by including contributions depending on the square of the electric-…
The SEHRS spectrum of 4,4' Bipyridine is analyzed on the base of the Dipole Quadrupole theory. It is demonstrated that there appear strong lines caused by vibrations transforming after a unit irreducible representation of the D2 symmetry group. which is most probably describes the symmetry properties of the molecule. These lines are nearly forbidden for the molecule, adsorbed on rough metal surface. Appearance of these lines is associated with a strong quadrupole light molecule interaction, which exists in this system. In addition, there are lines, caused by contributions from both the vibrati…
We present a general approach within the relativistic coupled-cluster theory framework to calculate exactly the first order wave functions due to any rank perturbation operators. Using this method, we calculate the static dipole and quadrupole polarizabilities in some alkali atoms and alkaline earth-metal ions. This may be a good test of the present theory for different rank and parity interaction operators. This shows a wide range of applications including precise calculations of both parity and CP violating amplitudes due to rank zero and rank one weak interaction Hamiltonians. We also give …
The rotational constants and the nitrogen nuclear quadrupole coupling constants of cis-3-aminophenol and trans-3-aminophenol are determined using Fourier-transform microwave spectroscopy. We examine several $J=2\leftarrow{}1$ and $1\leftarrow{}0$ hyperfine-resolved rotational transitions for both conformers. The transitions are fit to a rigid rotor Hamiltonian including nuclear quadrupole coupling to account for the nitrogen nucleus. For cis-3-aminophenol we obtain rotational constants of A=3734.930 MHz, B=1823.2095 MHz, and C=1226.493 MHz, for trans-3-aminophenol of A=3730.1676 MHz, B=1828.25…
A systematic investigation on vapor-liquid equilibria (VLE) of dipolar and quadrupolar fluids is carried out by molecular simulation to develop a new Helmholtz energy contribution for equations of state (EOS). Twelve two-center Lennard-Jones plus point dipole and point quadrupole model fluids (2CLJDQ) are studied for different reduced dipolar moments mu^{*2}=6,12, reduced quadrupolar moments Q^{*2}=2,4 and reduced elongations L^*=0, 0.505,1. Temperatures cover a wide range from about 55% to about 95% of the critical temperature of each fluid. The NpT + test particle method is used for the calc…
Searching for an accurate optical clock which can serve as a better time standard than the present day atomic clock is highly demanding from several areas of science and technology. Several attempts have been made to built more accurate clocks with different ion species. In this article we discuss the electric quadrupole and hyperfine shifts in the $5d^{9}6s^{2} ^{2}D_{5/2}(F=0,m_{F}=0)\leftrightarrow5d^{10}6s ^{2}S_{1/2}(F=2,m_{F}=0)$ clock transition in $ ^{199}Hg^{+}$, one of the most promising candidates for next generation optical clocks. We have applied Fock-space unitary coupled-cluster…
The recent detections of electric-quadrupole (E2) transitions in water vapor and magnetic-dipole (M1) transitions in carbon dioxide have opened a new field in molecular spectroscopy. While in their present status, the spectroscopic databases provide only electric-dipole (E1) transitions for polyatomic molecules (H2O, CO2, N2O, CH4, O3), the possible impact of weak E2 and M1 bands to the modeling of the Earth and planetary atmospheres has to be addressed. This is especially important in the case of carbon dioxide for which E2 and M1 bands may be located in spectral windows of weak E1 absorption…
Beyond the Electric Dipole Approximation: Electric and Magnetic Multipole Contributions Reveal Biaxial Water Structure from SFG Spectra at the Air-Water Interface
In this work, we propose new field-free estimators for static field-gradient polarizabilities in finite temperature PIMC simulation. Namely, dipole--quadrupole polarizability $A$, dipole--dipole--quadrupole polarizability $B$ and quadrupole--quadrupole polarizability $C$ are computed for several up to two-electron systems: H, H$^-$, He, Li$^+$, Be$^{2+}$, Ps$_2$, PsH, H$_2^+$, H$_2$, H$_3^+$ and HeH$^+$. We provide complementary data for ground state electronic properties within the adiabatic approximation, and demonstrate good agreement with available values in the literature. More importantl…
