The Physical Chemistry of Chirality

Hicks, Janice M.

doi:10.1021/bk-2002-0810.ch001

Cited by 12 publications

(16 citation statements)

References 37 publications

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“…SHG has been found to be extremely sensitive and highly versatile probe to investigate the chirality of molecules, solutions and thin films [33][34][35][36][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52], and more recently also in the study of metal nanostructures [18][19][20][21][22][23][24][25][26][27][28]. The sensitivity of SHG to chirality originates from its intrinsic sensitivity to symmetry properties.…”

Section: Chiral Probes Based On Second-harmonic Generationmentioning

confidence: 99%

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Nonlinear chiral imaging of subwavelength-sized twisted-cross gold nanodimers [Invited]

Huttunen

Bautista

Decker

et al. 2011

Opt. Mater. Express

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We perform second-harmonic generation (SHG) microscopy with circularly polarized (CP) light to measure chirality of individual twistedcross gold nanodimers. The chiral signatures, based on different SHG response for the two CP components of incident light, are clearly visible even with off-resonance excitation. The SHG responses of individual nanodimers are found to vary by about a factor of five. The technique thus has very high sensitivity to the nanoscale deformations of the structure. The chiral signatures of the dimers, however, are found to be more uniform, and the technique is thus able to recognize the handedness of the twisted nanodimers with high reliability.

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Section: Chiral Probes Based On Second-harmonic Generationmentioning

confidence: 99%

“…SHG has earlier been used to probe chiral properties of molecular films [33][34][35][36]. In the standard geometry of surface SHG, chirality leads to a different SHG response for the two CP components of fundamental light.…”

Section: Introductionmentioning

confidence: 99%

Nonlinear chiral imaging of subwavelength-sized twisted-cross gold nanodimers [Invited]

Huttunen

Bautista

Decker

et al. 2011

Opt. Mater. Express

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show abstract

“…However, other elements with an odd number of repeating indices (such as xxxy, zzxy), which vanish in this approximation due to isotropic symmetry, appear when the dipole approximation is relaxed. We have recently shown that these elements are chirally-sensitive i e appear only in chiral molecules ("handed" systems which are distinct from their mirror images [23,24]), and vanish in racemates, equal mixtures of molecules with opposite sense of chirality.…”

Section: Introductionmentioning

confidence: 99%

Time-domain chirally-sensitive three-pulse coherent probes of vibrational excitons in proteins

Abramavičius

Mukamel

2005

Chemical Physics

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The third order optical response of bosonic excitons is calculated using the Green's function solution of the Nonlinear Exciton Equations (NEE) which establish a quasiparticle-scattering mechanism for optical nonlinearities. Both time ordered and non ordered forms of the response function which represent time and frequency domain techniques, respectively, are derived. New components of the response tensor are predicted for isotropic ensembles of periodic chiral structures to first order in the optical wavevector. The nonlocal nonlinear response function is calculated in momentum space, where the finite exciton-exciton interaction length greatly reduces the computational effort. Applications are made to coupled anharmonic vibrations in the amide I infrared band of peptides. Chirally-sensitive and non sensitive signals for α helices and antiparallel β sheets are compared.

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“…[1][2][3][4] However, the interpretation of experimental spectral intensities is rather difficult because individual transitions are not resolved due to natural broadening of spectral lines. Also, the usual molecules of biological interest are rather big and flexible and interact strongly with the environment, which makes conventional theoretical descriptions difficult.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, complete understanding of the optical response, such as the vibrational spectrum, provides additional insight into other properties including molecular conformational behavior and interaction with the solvent and other molecules, or even to biological activity. 2,5,6 For infrared absorption (IR) and vibrational circular dichroism (VCD) the understanding is realized by simulation of observed frequencies and spectral intensities. Previously, very good results for larger molecular systems were achieved with semiempirical schemes for spectral simulations, such as the DeVoe polarizability theory 7,8 and other modifications of the coupled oscillator/ dipole coupling models.…”

Section: Introductionmentioning

confidence: 99%

Simulations of Structure and Vibrational Spectra of Deoxyoctanucleotides

et al. 2005

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Combined molecular dynamics and ab initio computations were applied for analysis of infrared absorption and vibrational circular dichroism spectra of deoxyoctanucleotides. Unlike for previous idealized models, molecular geometries of these shorter DNA fragments in solutions were obtained as dynamic averages from simulations in a periodic water box. Vibrational spectra for the whole octamers including hydrogen-bonded solvent molecules were simulated on the basis of density-functional calculations on small fragments and subsequent transfer of molecular property tensors. Explicit and continuum solvent models were compared. Apparently, the DNA segments retain an approximate B-conformation in the aqueous solutions, but the terminal base pairs significantly deviate from the planar arrangement and the vibrational circular dichroism spectrum for (CG) 2 nucleotide indicates a larger average helical twist. Sodium counterions moved freely around the molecule during the simulation and do not influence spectral intensities. Simulated absorption spectra faithfully reproduced the experimental signal of principal functional groups, while only qualitative agreement was obtained for the dependence on the basis sequence.

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The Physical Chemistry of Chirality

Cited by 12 publications

References 37 publications

Nonlinear chiral imaging of subwavelength-sized twisted-cross gold nanodimers [Invited]

Nonlinear chiral imaging of subwavelength-sized twisted-cross gold nanodimers [Invited]

Time-domain chirally-sensitive three-pulse coherent probes of vibrational excitons in proteins

Simulations of Structure and Vibrational Spectra of Deoxyoctanucleotides

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