the absorption modes arising from the sample environment opened the door to apply
this superb analytical technique to the electrochemical interface [6, 7]. The theoretical background on the propagation and reflection of the electromagnetic radiation
from a mirror surface, IRRAS and PM IRRAS as well as experimental considerations for in situ PM IRRAS with electrochemical control has been previously
summarized in [8–10].
Since the first application of PM IRRAS to probe the electrochemical interface,
potential-dependent molecular scale structural changes in species adsorbed on
metallic electrode surfaces have been described in the literature. The potentialdriven adsorption-desorption process of amphiphilic molecules on metallic electrode
surfaces has been correlated with the molecular scale rearrangements in mono- and
multilayer assemblies [11, 12]. Due to the availability of the molecular scale picture
of potential-dependent structural changes in thin organized films, in situ PM IRRAS
has found applications in bioelectrochemical studies [13–24]. Examination of the
structural changes in models of cell membranes exposed to changing electric fields
attract a significant scientific attention [15, 18, 20, 22–26]. Application of PM
IRRAS with electrochemical control to biomimetic studies was recently summarized
in [10, 27].
In situ PM IRRAS has been successfully applied to study structural changes
accompanying redox reactions in redox-active molecules in thin organized as well as
thick disordered molecular films present on metallic electrode surfaces [28–30]. A
significant limitation of in situ PM IRRAS is its applicability to metallic surfaces,
which reflect strongly the IR radiation. In the last years this problem was overcame.
Non-metallic electrode materials such as glassy carbon [31–34] or titanium
oxycarbide [35] have been successfully applied to PM IRRAS. Furthermore, it
was demonstrated that in situ PM IRRAS is an excellent analytical method for the
identification of products of complex catalytic reactions [31, 33]. The analysis of the
PM IRRA spectra from thick films, films adsorbing strongly the IR radiation or films
adsorbed on surfaces weakly reflecting the IR light may require special data treatment procedures [31].
PM IRRAS with electrochemical control is a dynamically developing technique,
which applicability to the investigation of complex electrochemical systems
increases. This monograph provides to the reader an introduction to the theory of
the IR light propagation in condensed media, theoretical background of IRRAS and
PM IRRAS spectroscopy (Chap. 2). It is followed by the description of potentialdriven changes in the composition, conformation and orientation of molecules
present in redox-inactive (Chap. 3) and redox-active (Chap. 4) films on electrode
surfaces.
References
1. Greenler RG (1966) Infrared study of adsorbed molecules on metal surfaces by reflection
techniques. J Chem Phys 44:310–314
References
3
this superb analytical technique to the electrochemical interface [6, 7]. The theoretical background on the propagation and reflection of the electromagnetic radiation
from a mirror surface, IRRAS and PM IRRAS as well as experimental considerations for in situ PM IRRAS with electrochemical control has been previously
summarized in [8–10].
Since the first application of PM IRRAS to probe the electrochemical interface,
potential-dependent molecular scale structural changes in species adsorbed on
metallic electrode surfaces have been described in the literature. The potentialdriven adsorption-desorption process of amphiphilic molecules on metallic electrode
surfaces has been correlated with the molecular scale rearrangements in mono- and
multilayer assemblies [11, 12]. Due to the availability of the molecular scale picture
of potential-dependent structural changes in thin organized films, in situ PM IRRAS
has found applications in bioelectrochemical studies [13–24]. Examination of the
structural changes in models of cell membranes exposed to changing electric fields
attract a significant scientific attention [15, 18, 20, 22–26]. Application of PM
IRRAS with electrochemical control to biomimetic studies was recently summarized
in [10, 27].
In situ PM IRRAS has been successfully applied to study structural changes
accompanying redox reactions in redox-active molecules in thin organized as well as
thick disordered molecular films present on metallic electrode surfaces [28–30]. A
significant limitation of in situ PM IRRAS is its applicability to metallic surfaces,
which reflect strongly the IR radiation. In the last years this problem was overcame.
Non-metallic electrode materials such as glassy carbon [31–34] or titanium
oxycarbide [35] have been successfully applied to PM IRRAS. Furthermore, it
was demonstrated that in situ PM IRRAS is an excellent analytical method for the
identification of products of complex catalytic reactions [31, 33]. The analysis of the
PM IRRA spectra from thick films, films adsorbing strongly the IR radiation or films
adsorbed on surfaces weakly reflecting the IR light may require special data treatment procedures [31].
PM IRRAS with electrochemical control is a dynamically developing technique,
which applicability to the investigation of complex electrochemical systems
increases. This monograph provides to the reader an introduction to the theory of
the IR light propagation in condensed media, theoretical background of IRRAS and
PM IRRAS spectroscopy (Chap. 2). It is followed by the description of potentialdriven changes in the composition, conformation and orientation of molecules
present in redox-inactive (Chap. 3) and redox-active (Chap. 4) films on electrode
surfaces.
References
1. Greenler RG (1966) Infrared study of adsorbed molecules on metal surfaces by reflection
techniques. J Chem Phys 44:310–314
References
3