AJP	ISSN : 0971 – 3093 Vol 25, No 2, February 2016

25^th Anniversary Year of AJP-2016

Prof. Dr. H. C. Wolfgang Kiefer

An Appreciation to Wolfgang Kiefer on the occasion of his 75^th birthday

Wolfgang Kiefer one of the most distinguished Raman spectroscopists will celebrate his 75^th birthday on February 12, 2016. It gives us great pleasure to dedicate him on this occasion the 2nd issue of 25th Anniversary of Asian Journal of Physics (ISSN 0971-3093).This anniversary issue contains eight contributions by friends, colleagues and former students of Wolfgang Kiefer. The contributions nicely feature the broad range of Raman spectroscopic approaches and their broad applicability.

Wolfgang Kiefer worked throughout his impressive scientific career for the further development of Raman spectroscopy and its application towards new scientific fields. Raman spectroscopy fascinated Wolfgang Kiefer already as a diploma and PhD student and was a solid companion throughout his scientific career. Wolfgang Kiefer developed and applied a great number of Raman approaches to unravel the structure of molecules in the gas, condensed and solid phase and on metal surfaces. In addition, the ultrafast dynamics taking place within and between these molecular systems took center stage of his scientific work.

Wolfgang Kiefer was born in 1941 in Pforzheim, Germany. He studied physics in Munich. After his PhD in 1970, he went for postgraduate studies to the National Research Council in Ottawa, Canada where he stayed for two years. He subsequently returned to Munich where he finished his habilitation in 1977. Between 1977 to 1984, Wolfgang Kiefer was a Professor in Bayreuth, Germany and from 1985 to 1988, he was appointed as full professor of Physics at the University of Graz, Austria. In 1988, he received a call for the chair for Physical Chemistry at the University of Wuerzburg, Germany, which he accepted. He stayed in Wuerzburguntil his retirement in 2006. Wolfgang Kiefer graduated 85 PhD students among them are twelve who also successfully pursued an academic career as Professor. The Kiefer Raman labs were throughout his scientific career an extremely popular meeting place, hosting a large number of friends and colleagues as well as students of many different countries who always have enjoyed the fruitful and also pleasant stays in the Kiefer group.

It is impossible and would go much beyond this brief editorial to comprehensively summarize the scientific achievements of Wolfgang Kiefer, which are published in 865 (!) publications. In the following, just some key words of his groundbreaking research are listed:

• Resonance Raman spectroscopy and development of theories for resonance Raman spectroscopy
• Atomic Raman spectroscopy
• Raman and Mie scattering from micro-particles
• Development of special techniques for linear and nonlinear Raman spectroscopy (e.g. Raman difference spectroscopy with rotating cell, Raman matrix isolation spectroscopy)
• Raman spectroscopy on:
  • Non-crystalline samples (e.g. glasses)
  • Nanostructures
  • Semiconductor quantum dots and quantum wires
  • Biological and biochemical samples
  • Polymers
  • Etc.
  • Surface enhanced Raman spectroscopy (SERS)
  • Raman- and IR spectroscopy in combination with density functional theory calculations on metal complexes
  • Nanosecond coherent anti-Stokes Raman spectroscopy (CARS)
  • Femtosecond coherent four-wave mixing spectroscopy (degenerate four-wave mixing = DFWM, CARS):
    • Ultrafast ground- and excited state dynamics in gases and condensed phase
    • Coherent control of vibrations

The eight contributions of this special issue nicely reflect this list of topics and deal with SERS, resonance Raman, theoretical concepts to interpret Raman spectra, Raman spectroscopy on glasses, femtosecond four-wave mixing spectroscopy, Raman spectroscopy in combination with DFT calculations. These contributions nicely show how Wolfgang Kiefer’s work inspired the authors and how he infected most of the senior authors with the “Raman gene”.

Raman spectroscopy has matured to become one of the most important laser spectroscopic methods and has found its way into almost all natural sciences. Raman spectroscopy has become an indispensable analytical method for physics, chemistry, mineralogy and also recently for the life sciences and medicine.It is not exaggerated to say that the work of Wolfgang Kiefer significantly contributed to this success story of Raman spectroscopy. It is too bad, that the inventor of Raman spectroscopy the great Indian scientist CV Raman is not able to witness the scientific impact his invention had and more importantly will still have even after more than 80 years of its discovery. However, he would be definitely very proud of what his “Raman followers” like Wolfgang Kiefer achieved and how they utilized his invention.

It is no surprise and more than deserved that Wolfgang Kiefer was awarded with the Raman Lifetime Award on the XXIV. International Conference on Raman Spectroscopy (ICORS 2014) in Jena. Despite this latest award, Wolfgang Kiefer received several more prestigious awards. Here, we would only like to mention the Pittsburg Spectroscopy Award and an Honorary Doctor degree from the University of Cluj-Napoca, Romania.

Although Wolfgang Kiefer is celebrating his 75^thbirthday, he is still “infected by the virus Raman spectroscopy”. In the basement of his house in the city of Eisingen he established a small but fine Raman lab he calls “Eisingen Laboratory for Applied Raman Spectroscopy” where he performs research work he always wanted to do but had no time for. Thus, for Wolfgang Kiefer Raman spectroscopy was not only his profession but also his hobby.

We hope that you will enjoy reading this 25th Anniversary of Asian Journal of Physics, which is dedicated to you.

Dear Wolfgang we wish you a happy 75^th birthday and lots more exciting research results from your Eisingen Laboratory for Applied Raman Spectroscopy! But most importantly we wish you good health, long life and prosperity in the circle of your family!

Jürgen Popp and Michael Schmitt on behalf of all authors and the editorial board of AJP.

Asian Journal of Physics, Vol  25 NO 2, 2016

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Vol. 25 No 2 (2016) 121-130

Two dimensional graphene derivatives supported isolated gold nanoparticles as an efficient SERS substrate

 

Shiju Abraham^a,b, Matthias König^b, Shobhit Pandey^c, Sunil K. Srivastava^d, Bernd Walkenfort^b, Anchal Srivastava^a*

^aDepartment of Physics, Banaras Hindu University, Varanasi, 221005, India

^bFaculty of Chemistry, University of Duisburg, 45141 Essen, Germany

^cMetallurgical Engineering Department, Indian Institute of Technology – (BHU), Varanasi

The present work accomplishes surface enhanced Raman scattering (SERS) studies using the combination of stable, diluted and isolated gold nanoparticles (Au NPs) of tailored size (~ 50 nm) and distribution on two dimensional carbon nanostructures (2D-CNS) i.e. graphene oxide (GO) and reduced graphene Oxide (RGO). Fabricated using a simple, quick and cost effective method, these SERS substrates have enough synergistic enhancement from each Au NPs and underlying CNS matrix with sensitivity enough to easily detect 10^-6 molar concentrations of analyte, 4-mercaptobenzoic acid (4-MBA). Further, uniform distribution of Au NPs ensures great reproducibility showing potential for standardization in future. © Anita Publications. All rights reserved.

Total Refs : 17

    1.    Marcano D C, Kosynkin D V, Berlin J M, Sinitskii A, Sun Z, Slesarev A, Alemany L B, Lu W, Tour J M,ACS Nano;4 (2010) 4806.
    2.    Li D, Müller M B, Gilje S, Kaner R B, Wallace G G, Nat Nanotechnol, 3 (2008)101.
    3.    Perrault S D, Chan W C W, J Am Chem Soc,;131 (2009) 17042.
    4.    Park S, An J, Potts J R, Velamakanni A, Murali S, Ruoff R S, Carbon, 49 (2011) 3019.

 Vol. 25 No 2 (2016) 131-136

Encapsulation of optical gratings using nanoporous alumina layers

 

Lilit Ghazaryan, Ernst-Bernhard Kley, Adriana Szeghalmi*

In this work, we describe a method to encapsulate optical gratings with nanoporous Al₂O₃. The encapsulation process consists of covering a grating, filled with a sacrificial material, by an organic-inorganic thin alucone layer. The element is than heated upto 400 °C to remove the organic component from the alucone film. The nanoporous Al₂O₃ film, formed after the removal of the organic component acts as a diffusion layer for the decomposition products of the sacrificial material. The complete removal of the sacrificial material was confirmed by energy dispersive x-ray spectroscopy (EDX). © Anita Publications. All rights reserved.
Keywords: Optical gratings, Energy dispersive x-ray spectroscopy (EDX).

Total Refs : 20

 Vol. 25 No 2 (2016) 137-156

Mechanism of Intramolecular Multi-Electron Photochemistry in a 4H-Imidazole Ruthenium Dye

 

Linda Zedler,^1,2 Stephan Kupfer,² Sven Krieck,³ Rainer Beckert,⁴ Sven Rau,⁵ Michael Schmitt,² Jürgen Popp,^1,2 Benjamin Dietzek^1,2

¹ Institute of Photonic Technology Jena (IPHT), Albert-Einstein-Straße 9, 07745 Jena, Germany

² Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-University Jena, Helmholtzweg 4, 07743 Jena, Germany

³ Institute of Inorganic and Analytical Chemistry, Friedrich-Schiller-University Jena, Humboldtstraße 8, 07743 Jena, Germany

⁴ Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Humboldtstraße 10, 07743 Jena, Germany

Ruthenium complexes containing a 4H-imidazole chromophore feature a spectrally extremely broad absorption in the UV-Vis and near IR spectral range. In addition, those complexes show a notable redox activity and high chemical stability. These important characteristics render these systems promising for electron storage and inter-molecular electron transfer. But in order to improve the function of electron transfer or storage by modifying the structure, photo-induced structural changes and charge transfer processes with the molecular functionality need to be correlated. This includes also a fundamental understanding of relevant photo-excited states, complex stability and reaction pathways, particularly for multiple electron transfer steps in order to identify parasitic processes, which delimitate the functionality. However, the reactivity and short lifetime of electronically excited complexes renders the detailed spectroscopic characterization cumbersome. In this contribution the combination of spectroscopic tools with the electrochemical preparation of single and double reduced states is used to model the long-time behavior of photo-activated complexes. Specifically, UV-Vis and resonance Raman spectroscopy is performed to investigate a four times quasi-reversible reducible ruthenium complex and the results are analyzed using computational methods. © Anita Publications. All rights reserved.

Keywords: Ruthenium complexes,  4H-imidazole, Chromophore, Redox activity, Life time, UV-Vis  and Resonance Raman spectroscopy.

Total Refs : 30

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 Vol. 25 No 2 (2016) 157-165

Dehydration of 3-octanol studied by 2D Raman, IR and NMR hetero correlation spectroscopy

 

Robby Fritzsch^a, Robert Geitner^a, Thomas W. Bocklitz^a, Benjamin Dietzek^a,c, Micheal Schmitt^a and Jürgen Popp^a,b,c

^a Institute for Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.

^b Jena Center of Soft Matter (JCSM), Friedrich Schiller University Jena, Philosophenweg 7,07743, Jena, Germany

2D correlation spectroscopy is a useful technique for analyzing chemical reactions. We studied the acid catalyzed dehydration of 3‑octanol at 150 °C with FT‑Raman, FT‑ATR‑IR and ¹H‑NMR and evaluated the use of 2D correlation spectroscopy in particular the correlation of spectroscopic data from different methods with one another. This 2D hetero correlation approach proved to be useful in validating the signal assignment but otherwise limited in use. We could also show that all four possible octene isomers are forming over the course of the reaction. © Anita Publications. All rights reserved.

Total Refs : 20

 Vol. 25 No 2 (2016) 167-177

Isotopic Effects in (Surface Enhanced) Raman Spectroscopy – Single Molecule Aspects

 

Stephan Kupfer,¹ Volker Deckert,^1,2 Stefanie Gräfe¹

¹ Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-University Jena, Helmholtzweg 4, 07743 Jena, Germany

Generally, isotopic effects are of minor importance in standard vibrational spectroscopy, this is in particular the case, if the signal originates form a macroscopic sample. Consequently, an average spectrum with respect to the natural isotopic redundancy is obtained. However, for state-of-the-art high-resolution techniques, e.g. surface-enhanced Raman spectroscopy, where only a small number of molecules (or even merely a single molecule) are the focus of the exciting beam, isotopic effects can have a considerable influence on the spectral pattern. Here we present a computational study investigating such isotopic effects on the Raman spectrum for the ¹³C isotope in the thiophenol molecule. Therefore, the Raman spectra of all four possible singly ¹³C doped species are calculated at the density functional theory level of theory and compared to the undoped thiophenol reference spectrum. The impact of ¹³C substitution on the vibrational frequencies as well as on the Raman intensities is rationalized. In particular large effects are determined for the in plane vibrational modes, while each of the five calculated species (one undoped and 4 singly doped) features a unique Raman intensity pattern. © Anita Publications. All rights reserved.

Keywords: Isotopic effects, Laser pulses, Thiophenol, Surface-enhanced Raman spectroscopy (SERS)

Total Refs : 32

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 Vol. 25 No 2 (2016) 179-187

Binary heavy metal bismuthate glass-ceramics with classical glass forming oxide

 

S Simon, M Muresan-Pop, C Leordean, M Baia, L Baia

As-prepared and heat treated heavy metal binary system of bismuth oxide with classical glass forming oxides were investigated with respect to their ability to form vitreous structure in the composition range of sillenite. For this high ratio of bismuth to classical glass former cation Bi/M =12 (M = Si, Ge or B), the X-ray diffraction analysis of as-prepared samples points out δ-Bi₂O₃ nanocrystalline phase separation, while FTIR and Raman spectroscopic analysis provide typical features for the vitreous state, with no feature of crystalline phase. After heat treatment Bi₁₂MO_20-δ sillenite crystalline phases are identified in all samples, and the structural changes induced by sillenites development are clearly revealed in FTIR and Raman spectra. A new attempt for structural units assignment based on analysis of vibrational spectra recorded from heavy metal bismuthate glass-ceramic systems with classical glass forming oxides is presented. © Anita Publications. All rights reserved.

Total Refs : 22

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6.   Baia L, Stefan R, Kiefer W, Popp J, Simon S, J Non-Cryst Solids, 303(2002)379-386.

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 Vol. 25 No 2 (2016) 189-198

Femtosecond time-resolved four-wave mixing spectroscopy of coupled electron-nuclear motion

 

Julian Albert^a and Volker Engel^a

^a Institute for Physical and Theoretical Chemistry, University Würzburg, Emil-Fischer-Str. 42, 97074, Würzburg, Germany.

e-mail: [email protected]

We present a theoretical study of time-resolved four-wave mixing (FWM) spectroscopy on a model system describing coupled electron-nuclear dynamics. Changing the parameterization of the Coulomb-interaction, two situation can be created. In one case, the Born-Oppenheimer adiabatic approximation holds. In adjusting the pulse sequence it is then possible to separately monitor ground state and excited state vibrational wave-packet dynamics. In the second case, strong nonadiabatic coupling is present so that the separation of ground- and excited state nuclear dynamics becomes difficult. To investigate details of the dynamics and its relation to the spectroscopy, we compare FWM-signals obtained from an exact numerical calculation to those obtained within the adiabatic approximation. © Anita Publications. All rights reserved.

Keywords: Femtosecond,  Laser pulses, Emission, Born-Oppenheimer approximation Time-resolved four-wave mixing (FWM) spectroscopy

Total Refs : 33

Vol. 25 No 2 (2016) 199-229

The accuracy of the M06L DFT method in the prediction of the vibrational Spectra of 4-amino-2-chlorobenzonitrile:A detailed interpretation of the Molecular Structure and vibrational IR and Raman spectra and other molecular properties using several DFT methods

 

M Alcolea Palafox^a, Rachna Rastogi^b*, Anupama^c, M Jane Alam^d, Daisy Bhat^b, V K Rastogi^b,e

^a Nofima AS – the Norwegian Institute of Food, Fisheries and Aquaculture Research, PB 210, N-1431 Ås, Norway.

^b Internet Lab, R D Group of Institutions, NH-58, Kadarabad (Modinagar), Ghaziabad, India.

^c Department of Chemistry, SRM University, NCR Campus, Modinagar-201 204, India.

^d Department of Physics, Aligarh Muslim University, Aligarh, India.

The accuracy of the M06L DFT method in the prediction of the vibrational spectra of 4-amino-2-chlorobenzonitrile molecule was tested and compared with that of the B3LYP method. Its experimental FT-IR and FT- Raman spectra in the solid state were recorded at room temperature, and the bands assigned with accuracy by comparison with the results obtained by different methods, including MP2 and DFT. The FT-IR spectrum in Nujol mull was also recorded and analyzed. Several scaling procedures were used and several recommendations were presented. The wavenumbers of most of the modes were found in the expected range and the error obtained was in general very low. The thermodynamic parameters were calculated and discussed. The NBO analysis was done and Molecular Electrostatic Potential (MEP) was plotted. The calculated HOMO and LUMO energies showed that charge transfer occurs within the molecule. Several general conclusions were deduced. © Anita Publications. All rights reserved.

Keywords: M06L DFT method; FT-IR and FT- Raman spectra; Molecular Electrostatic Potential (MEP); HOMO and LUMO.

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The accuracy of the M06L DFT method in the prediction of the vibrational Spectra….pdf