The study of spectral diffusion of an electronic transition of a molecule in an amorphous host yields information on the structural relaxation of the system. Although this phenomenon has recently been investigated by many groups, no unambiguous picture has yet emerged as regards the dynamics of glasses at low temperature. Furthermore, the relation between spectral diffusion and energy transfer resulting from a concentration increase has so far not been addressed.
{"title":"The Effect of Pressure, Time and Concentration in Hole-Burning Studies","authors":"S. Volker","doi":"10.1364/shbs.1994.thc2","DOIUrl":"https://doi.org/10.1364/shbs.1994.thc2","url":null,"abstract":"The study of spectral diffusion of an electronic transition of a molecule in an amorphous host yields information on the structural relaxation of the system. Although this phenomenon has recently been investigated by many groups, no unambiguous picture has yet emerged as regards the dynamics of glasses at low temperature. Furthermore, the relation between spectral diffusion and energy transfer resulting from a concentration increase has so far not been addressed.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"130388414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The concept of the homogeneous spectral linewidth of an impurity center is more complicated in disordered media such as organic glasses and polymers than it is in crystals. In amorphous media the local environments for impurity centers are continuously changing with time. As a result transition frequencies of individual centers diffuse within the inhomogeneous broadened spectral contour, which is called spectral diffusion. When the timescale for spectral diffusion processes is much longer than the dephasing time, it is possible to distinguish homogeneous dephasing from spectral diffusion. On the other hand, when the timescales of spectral diffusion and dephasing processes are comparable these phenomena become indistinguishable.
{"title":"Linewidths In Spectra Of Terrylene In Polyethylene Probed By Incoherent Photon Echo. Comparison With Single Molecule Spectroscopy Data","authors":"N. Gruzdev, R. I. Personov, Y. Vainer","doi":"10.1364/shbs.1994.wd2","DOIUrl":"https://doi.org/10.1364/shbs.1994.wd2","url":null,"abstract":"The concept of the homogeneous spectral linewidth of an impurity center is more complicated in disordered media such as organic glasses and polymers than it is in crystals. In amorphous media the local environments for impurity centers are continuously changing with time. As a result transition frequencies of individual centers diffuse within the inhomogeneous broadened spectral contour, which is called spectral diffusion. When the timescale for spectral diffusion processes is much longer than the dephasing time, it is possible to distinguish homogeneous dephasing from spectral diffusion. On the other hand, when the timescales of spectral diffusion and dephasing processes are comparable these phenomena become indistinguishable.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"130806766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
At very low temperatures, the spread in the different environments of matrix embedded dye molecules results in an inhomogeneously broadened S1 ← S0 band. Spectroscopic techniques based on the appearence of optical zero phonon lines, such as fluorescence line narrowing, spectral hole-burning, and single molecule spectroscopy provide an experimental resolution limited by the homogeneous linewidth. From the investigation of the homogeneous line width as a function of different parameters (time, temperature) information on the guest host interactions responsible for the observed linewidth is obtained. Spectrally narrow features are extremely sensitive probes for external perturbations, such as electric fields, magnetic fields, or hydrostatic pressure.
{"title":"Spectral Hole Burning: Data Storage and Processing","authors":"U. Wild, E. Maniloff, S. Bernet, A. Renn","doi":"10.1364/shbs.1994.wa1","DOIUrl":"https://doi.org/10.1364/shbs.1994.wa1","url":null,"abstract":"At very low temperatures, the spread in the different environments of matrix embedded dye molecules results in an inhomogeneously broadened S1 ← S0 band. Spectroscopic techniques based on the appearence of optical zero phonon lines, such as fluorescence line narrowing, spectral hole-burning, and single molecule spectroscopy provide an experimental resolution limited by the homogeneous linewidth. From the investigation of the homogeneous line width as a function of different parameters (time, temperature) information on the guest host interactions responsible for the observed linewidth is obtained. Spectrally narrow features are extremely sensitive probes for external perturbations, such as electric fields, magnetic fields, or hydrostatic pressure.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"130947856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photochemical holes can be burned at relatively high temperatures in the Qx band of a free base porphyrin with ionic substituents when the molecule is dispersed in polyvinylalcohol (PVA) [1-2]. This characteristics of the porphyrin-PVA system is due to the facts that the Debye-Waller factor is relatively large [3] and the thermally activated backward reaction is small [4], Figure 1(a) shows one of such porphyrin molecules, TCPP(Na). The large Debye-Waller factor in porphyrin-PVA system is a direct consequence of a high mean phonon frequency. The typical phonon energy of the porphyrin-PVA system, which was determined as the energy deference between the zero-phonon hole and the bottom of the side hole, is as large as 25 cm–1. According to ref. 3, the Debye-Waller factor f(T) of porphyrin-PVA system is well represented by one-phonon approximation.
{"title":"Photochemical Hole Burning and Debye-Waller Factor in Polyvinylalcohol doped with Ionic Porphyrins","authors":"K. Sakoda, Masayuki Maeda","doi":"10.1364/shbs.1994.wd38","DOIUrl":"https://doi.org/10.1364/shbs.1994.wd38","url":null,"abstract":"Photochemical holes can be burned at relatively high temperatures in the Qx band of a free base porphyrin with ionic substituents when the molecule is dispersed in polyvinylalcohol (PVA) [1-2]. This characteristics of the porphyrin-PVA system is due to the facts that the Debye-Waller factor is relatively large [3] and the thermally activated backward reaction is small [4], Figure 1(a) shows one of such porphyrin molecules, TCPP(Na). The large Debye-Waller factor in porphyrin-PVA system is a direct consequence of a high mean phonon frequency. The typical phonon energy of the porphyrin-PVA system, which was determined as the energy deference between the zero-phonon hole and the bottom of the side hole, is as large as 25 cm–1. According to ref. 3, the Debye-Waller factor f(T) of porphyrin-PVA system is well represented by one-phonon approximation.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"129714080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A theoretical method that systematically finds tunneling systems in glasses and allows a microscopic justification of the standard tunneling model of Phillips and Anderson, Halperin and Varma is presented. The calculation shows that the major assumptions of the tunneling model are qualitatively correct; however, there are small deviations in the distribution functions of tunneling parameters that give rise to the T1+ε law for specific heat and the T2-α law for the thermal conductivity. The calculation also allows a quantitative estimate of the interaction of the two level systems with phonons (the deformation potential). The calculations confirm the weak coupling picture, in contrast with recent conjectures. The theory is then mapped onto all structural glasses via a Lennard-Jones model for the interaction between sub-units in the glass. These sub-units are molecular systems (e.g monomers in a polymer glass or tetrahedra in silicate glasses). From this mapping, we find that the tunneling parameters, and hence the thermal properties, of most structural glasses can be estimated semi-quantitatively from the microscopic parameters of the Hamiltonian. A further argument allows the connection between the tunneling parameters and the macroscopic experimental properties (sound velocity and density) to be drawn. The calculations also go smoothly into the "soft potential" model that explains the thermal behavior at higher temperatures (~10K), thus providing a universal model. From these calculations, the distribution of tunneling rates that give rise to spectral diffusion can be calculated and compared to recent experiments. These will be presented at the conference, along with calculations of the effect on the two level system distributions of introducing an impurity (i.e. chromophore) into the glass.
{"title":"Low Temperature Properties of Glasses: Two Level Systems, Soft Modes, and Spectral Diffusion","authors":"R. Silbey, A. Heuer, D. Dab","doi":"10.1364/shbs.1994.the1","DOIUrl":"https://doi.org/10.1364/shbs.1994.the1","url":null,"abstract":"A theoretical method that systematically finds tunneling systems in glasses and allows a microscopic justification of the standard tunneling model of Phillips and Anderson, Halperin and Varma is presented. The calculation shows that the major assumptions of the tunneling model are qualitatively correct; however, there are small deviations in the distribution functions of tunneling parameters that give rise to the T1+ε law for specific heat and the T2-α law for the thermal conductivity. The calculation also allows a quantitative estimate of the interaction of the two level systems with phonons (the deformation potential). The calculations confirm the weak coupling picture, in contrast with recent conjectures. The theory is then mapped onto all structural glasses via a Lennard-Jones model for the interaction between sub-units in the glass. These sub-units are molecular systems (e.g monomers in a polymer glass or tetrahedra in silicate glasses). From this mapping, we find that the tunneling parameters, and hence the thermal properties, of most structural glasses can be estimated semi-quantitatively from the microscopic parameters of the Hamiltonian. A further argument allows the connection between the tunneling parameters and the macroscopic experimental properties (sound velocity and density) to be drawn. The calculations also go smoothly into the \"soft potential\" model that explains the thermal behavior at higher temperatures (~10K), thus providing a universal model. From these calculations, the distribution of tunneling rates that give rise to spectral diffusion can be calculated and compared to recent experiments. These will be presented at the conference, along with calculations of the effect on the two level system distributions of introducing an impurity (i.e. chromophore) into the glass.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"121534189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The temperature cycling hole-burning experiment is a good means to study the irreversible structural relaxation in disordered materials [1,2]. By observing the hole shape as well as the hole area and the hole width carefully, we investigated the relaxation of two-level-systems (TLS) that is characteristic of protein.
{"title":"Non - Lorentzian hole shape induced by spectral diffusion in H2-protoporphyrin substituted myoglobin","authors":"Y. Shibata, A. Kurita, T. Kushida","doi":"10.1364/shbs.1994.wd12","DOIUrl":"https://doi.org/10.1364/shbs.1994.wd12","url":null,"abstract":"The temperature cycling hole-burning experiment is a good means to study the irreversible structural relaxation in disordered materials [1,2]. By observing the hole shape as well as the hole area and the hole width carefully, we investigated the relaxation of two-level-systems (TLS) that is characteristic of protein.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"124145184","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. Polívka, D. Engst, J. Dian, P. Kroh, J. Pšenčík, M. Vácha, L. Nedbal, Werner Vermaas, J. Hála
Spectral hole-burning is powerful tool for the study of fast relaxation processes (e.g. excited energy transfer - EET, electron transport - e.t.) in photosynthetic systems. Fast e.t. was systematically studied by transient hole-burning (THB) in absorption spectra of reaction centra in purple bacteria and green plants [1]. The THB in fluorescence of PSII particles was described in [2]. Persistent spectral hole-burning (PSHB) enabled to determine the hole-burning mechanism, the EET rate constants, electron-phonon coupling and frequency of protein phonons. The PSHB in fluorescence has been measured in antenna complexes: CP43 and CP47 of PSII [3], B800-850 of purple photosynthetic bacteria [4] and in chlorosomes of green sulphur photosynthetic bacteria [5]. Laser induced hole filling in fluorescence spectra of CP43 of PSII was presented recently in [6]. These data were obtained using wild type organisms. Here, we report an investigation of EET by fluorescence PSHB in photosynthetic antenna using H114Q mutation in the CP47 complex of Synechocystis sp. PCC 6803.
{"title":"Persistent Spectral Hole Burning In The Antenna Protein CP47 Of Synechocystis SP. Mutant H114Q","authors":"T. Polívka, D. Engst, J. Dian, P. Kroh, J. Pšenčík, M. Vácha, L. Nedbal, Werner Vermaas, J. Hála","doi":"10.1364/shbs.1994.wd18","DOIUrl":"https://doi.org/10.1364/shbs.1994.wd18","url":null,"abstract":"Spectral hole-burning is powerful tool for the study of fast relaxation processes (e.g. excited energy transfer - EET, electron transport - e.t.) in photosynthetic systems. Fast e.t. was systematically studied by transient hole-burning (THB) in absorption spectra of reaction centra in purple bacteria and green plants [1]. The THB in fluorescence of PSII particles was described in [2]. Persistent spectral hole-burning (PSHB) enabled to determine the hole-burning mechanism, the EET rate constants, electron-phonon coupling and frequency of protein phonons. The PSHB in fluorescence has been measured in antenna complexes: CP43 and CP47 of PSII [3], B800-850 of purple photosynthetic bacteria [4] and in chlorosomes of green sulphur photosynthetic bacteria [5]. Laser induced hole filling in fluorescence spectra of CP43 of PSII was presented recently in [6]. These data were obtained using wild type organisms. Here, we report an investigation of EET by fluorescence PSHB in photosynthetic antenna using H114Q mutation in the CP47 complex of Synechocystis sp. PCC 6803.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"115320258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
When a sequence of temporally modulated optical waveforms illuminate an inhomogeneously broadened absorbing medium, the resultant optical coherent transient output signal's represents the cross-correlation or convolution of the input temporal waveforms.1 The projected performance characteristics of coherent transient processors include data rates greater than 10 GHz, time-bandwidth products far in excess of 10,000, and the ability to fully process both amplitude and phase modulated waveforms.1,2 Previously it was assumed that the input data stream and pattern stream must both be shorter than the absorbing transition's homogeneous dephasing time and must both be reentered in order to process longer or multiple data streams.1 It has recently been proposed that patterns could be permanently stored in an inhomogeneously broadened solid and that input data streams of indefinite length could be continuously processed in real time without the need to reenter the input pattern.3,4 In this paper, we present a proof of concept demonstration of an optical coherent transient continuous correlator.
{"title":"Coherent Transient Continuous Optical Processing in a Solid","authors":"Miao Zhu, C. M. Jefferson, W. Babbitt","doi":"10.1364/shbs.1994.fd4","DOIUrl":"https://doi.org/10.1364/shbs.1994.fd4","url":null,"abstract":"When a sequence of temporally modulated optical waveforms illuminate an inhomogeneously broadened absorbing medium, the resultant optical coherent transient output signal's represents the cross-correlation or convolution of the input temporal waveforms.1 The projected performance characteristics of coherent transient processors include data rates greater than 10 GHz, time-bandwidth products far in excess of 10,000, and the ability to fully process both amplitude and phase modulated waveforms.1,2 Previously it was assumed that the input data stream and pattern stream must both be shorter than the absorbing transition's homogeneous dephasing time and must both be reentered in order to process longer or multiple data streams.1 It has recently been proposed that patterns could be permanently stored in an inhomogeneously broadened solid and that input data streams of indefinite length could be continuously processed in real time without the need to reenter the input pattern.3,4 In this paper, we present a proof of concept demonstration of an optical coherent transient continuous correlator.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"116117964","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
K. Kamitani, M. Uo, H. Inoue, A. Makishima, T. Suzuki, K. Horie
We have reported the incorporation of the photochemical hole-burning (PHB) dyes to the silica gels and the observation of spectral holes [1-3]. The porphyrins are well-known PHB dyes. However, in acidic solutions, many porphyrins change their forms into dication which is inactive in PHB [4]. So we have developed two-step sol-gel processes from the hydrolysis of TMOS with NaOH, and successfully incorporated free-base TPPS, a kind of porphyrin, in the silica gels [5].
{"title":"Synthesis and Spectroscopy of TPP Derivative-Doped Silica Gels by Sol-Gel Process","authors":"K. Kamitani, M. Uo, H. Inoue, A. Makishima, T. Suzuki, K. Horie","doi":"10.1364/shbs.1994.wd56","DOIUrl":"https://doi.org/10.1364/shbs.1994.wd56","url":null,"abstract":"We have reported the incorporation of the photochemical hole-burning (PHB) dyes to the silica gels and the observation of spectral holes [1-3]. The porphyrins are well-known PHB dyes. However, in acidic solutions, many porphyrins change their forms into dication which is inactive in PHB [4]. So we have developed two-step sol-gel processes from the hydrolysis of TMOS with NaOH, and successfully incorporated free-base TPPS, a kind of porphyrin, in the silica gels [5].","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"127371471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
W. Moerner, A. Myers, P. Tchénio, D. Pohl, B. Hecht, T. Plakhotnik, T. Irngartinger, U. Wild
This talk describes three topics in single-molecule spectroscopy in solids, the observation of the vibrational modes of a single molecule, an improved analysis of the saturation behavior, and progress toward near-field single-molecule spectroscopy at low temperatures.
{"title":"Recent Advances in Single-Molecule Spectroscopy in Solids: Vibrational Modes, Improved Saturation Analysis, and Near-Field Excitation at Low Temperatures","authors":"W. Moerner, A. Myers, P. Tchénio, D. Pohl, B. Hecht, T. Plakhotnik, T. Irngartinger, U. Wild","doi":"10.1364/shbs.1994.wb2","DOIUrl":"https://doi.org/10.1364/shbs.1994.wb2","url":null,"abstract":"This talk describes three topics in single-molecule spectroscopy in solids, the observation of the vibrational modes of a single molecule, an improved analysis of the saturation behavior, and progress toward near-field single-molecule spectroscopy at low temperatures.","PeriodicalId":443330,"journal":{"name":"Spectral Hole-Burning and Related Spectroscopies: Science and Applications","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"122325619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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