Density-functional theory of linear and nonlinear time-dependent molecular properties

Sałek, Paweł; Vahtras, Olav; Helgaker, Trygve; Ågren, Hans

doi:10.1063/1.1516805

Cited by 373 publications

(285 citation statements)

References 67 publications

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“…(50) and (51) of Ref. 54. The construction of the property gradients η ±ω of the field-matter interaction operator requires the evaluation of integrals of the form…”

Section: Methodsmentioning

confidence: 99%

Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation

List

Kauczor

Saue

et al. 2015

The Journal of Chemical Physics

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Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation, 2015, Journal of Chemical Physics, (142) We present a formulation of molecular response theory for the description of a quantum mechanical molecular system in the presence of a weak, monochromatic, linearly polarized electromagnetic field without introducing truncated multipolar expansions. The presentation focuses on a description of linear absorption by adopting the energy-loss approach in combination with the complex polarization propagator formulation of response theory. Going beyond the electric-dipole approximation is essential whenever studying electric-dipole-forbidden transitions, and in general, non-dipolar effects become increasingly important when addressing spectroscopies involving higher-energy photons. These two aspects are examined by our study of the near K-edge X-ray absorption fine structure of the alkaline earth metals (Mg, Ca, Sr, Ba, and Ra) as well as the trans-polyenes. In following the series of alkaline earth metals, the sizes of non-dipolar effects are probed with respect to increasing photon energies and a detailed assessment of results is made in terms of studying the pertinent transition electron densities and in particular their spatial extension in comparison with the photon wavelength. Along the series of trans-polyenes, the sizes of non-dipolar effects are probed for X-ray spectroscopies on organic molecules with respect to the spatial extension of the chromophore. C 2015 AIP Publishing LLC.[http://dx

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“…(50) and (51) of Ref. 54. The construction of the property gradients η ±ω of the field-matter interaction operator requires the evaluation of integrals of the form…”

Section: Methodsmentioning

confidence: 99%

Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation

List

Kauczor

Saue

et al. 2015

The Journal of Chemical Physics

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“…In the latter, implementations of quadratic response functions were employed for the Hartree-Fock (HF), density-functional theory (DFT), and coupled-cluster (CC) methods from Refs. [26][27][28], respectively. DFT was used to obtain results of predictive quality for larger molecules.…”

mentioning

confidence: 99%

Observation of Optical Chemical Shift by Precision Nuclear Spin Optical Rotation Measurements and Calculations

Shi¹,

Ikäläinen

Vaara

et al. 2013

J. Phys. Chem. Lett.

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*Nuclear spin optical rotation (NSOR) is a recently developed technique for detection of nuclear magnetic resonance via rotation of light polarization, instead of the usual long-range magnetic fields. NSOR signals depend on hyperfine interactions with virtual optical excitations, giving new information about the nuclear chemical environment. We use a multi-pass optical cell to perform first precision measurements of NSOR signals for a range of organic liquids and find clear distinction between proton signals for different compounds, in agreement with our earlier predictions. Detailed first principles quantum-mechanical NSOR calculations are found to be in good agreement with the measurements. The effect of light on nuclear magnetic resonance (NMR) has been the subject of considerable interest, as it can be used to further increase the power of NMR spectroscopy [1,2]. While NMR frequency shifts due to laser light turned out to be too small to be easily measured [3], the inverse effect of optical rotation (OR) caused by nuclear spin polarization was observed in water and liquid 129 Xe [4]. The rotation of light polarization is similar to the Faraday effect caused by nuclear magnetization, but is enhanced by the hyperfine interaction between nuclear spins and virtual electronic excitations. Recent firstprinciples calculations of the nuclear spin OR (NSOR) predict different signals from chemically non-equivalent nuclei, opening the possibility of a new chemical analysis technique combining optical and NMR spectroscopy [5]. However, the signal-to-noise ratio (SNR) of NSOR detection has been poor in the first experiments utilizing low-field CW NMR [4] and in high-field pulsed experiments [6,7]. NSOR differences between the same nuclei in different molecular positions have not been clearly observed [7].Here we use a multi-pass optical cell [8,9] to measure proton NSOR with an SNR greater than 15 after 1000 seconds of integration and perform systematic NSOR measurements on organic liquids with absolute uncertainty of 5%. Contrary to recent report [7], we find that the NSOR signals do not scale with the Verdet constant V of the liquid since the hyperfine interaction between electrons and nuclei is influenced by the chemical environment. The ratio of NSOR to Faraday rotation and to inductive 1 H signals ranges by more than a factor of 2 for the simple chemicals studied. We also apply the recent first-principles theoretical method [5] for calculation of NSOR and obtain results in good qualitative agreement with our measurements for both 1 H and 19 F spins.

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“…It is the generic nature of the AO-based response theory that allows us to calculate molecular properties in a manner that is transparent to the underlying reference wave function. The evaluation of the XC functional derivatives has previously been described in the context of perturbationindependent basis sets by Sałek et al [67] and, in the specific case of magnetic-field perturbed densities, by Krykunov et al [68] and by Kjaergaard et al [69]. A general strategy for the evaluation of higher-order perturbed XC energies and functionals is given in Ref.…”

Section: Atomic-orbital-basis Kohn-sham Densityfunctional Response Thmentioning

confidence: 99%

Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

et al. 2011

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We present the first relativistic study of the electric-field-gradient induced birefringence (Buckingham birefringence), with application to the series of molecules CX 2 (X = O, S, Se, Te). A recently developed atomicorbital-driven scheme for the calculation of time-dependent molecular properties using one-, two-and four-component relativistic wave functions (Bast et al. in Chem Phys 356:177, 2009) is extended to first-order frequencydependent magnetic-field perturbations, using London atomic orbitals to ensure gauge-origin independent results and to improve basis-set convergence. Calculations are presented at the Hartree-Fock and Kohn-Sham levels of theory and results for CO 2 and CS 2 are compared with previous high-level coupled-cluster calculations. Except for the heaviest member of the series, relativistic effects are small-in particular for the temperature-independent contribution to the birefringence. By contrast, the effects of electron correlation are significant. However, the reliability of standard exchange-correlation functionals in describing Buckingham birefringence remains unclear based on the comparison with high-level coupled-cluster singles-anddoubles calculations.

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Density-functional theory of linear and nonlinear time-dependent molecular properties

Cited by 373 publications

References 67 publications

Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation

Beyond the electric-dipole approximation: A formulation and implementation of molecular response theory for the description of absorption of electromagnetic field radiation

Observation of Optical Chemical Shift by Precision Nuclear Spin Optical Rotation Measurements and Calculations

Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

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