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Molecular Spectroscopy: Absorption and Emission

Molecular Spectroscopy: Absorption and Emission

Molecules possess discrete energy levels called quantum states. Unlike atoms, which have simpler energy levels, molecules possess additional rotational and vibrational energy levels. Each energy level is separated by an energy gap, with the gaps between adjacent electronic, vibrational, and rotational levels varying significantly. The three types of energy levels in a diatomic molecule are shown in Figure 1.

IR Spectroscopy: Molecular Vibration Overview

IR Spectroscopy: Molecular Vibration Overview

When Infrared (IR) radiation passes through a covalently bonded molecule, the bonds transition from lower to higher vibrational levels. The fundamental vibrational motions that result in infrared absorption can be classified as stretching or bending vibrations.
Stretching vibrations are vibrational motions that occur along the bond line, changing the bond length or distance between two bonded atoms. They are further distinguished as symmetric or asymmetric. In symmetric stretching, the...

Deactivation Processes: Jablonski Diagram

Deactivation Processes: Jablonski Diagram

Luminescence, the emission of light by a substance that has absorbed energy, is a process that involves the interaction of molecules with light. The energy-level diagram, or Jablonski diagram, is a graphical representation of these interactions, illustrating the various states and transitions a molecule can undergo. In a typical Jablonski diagram, the lowest horizontal line represents the ground-state energy of the molecule, which is usually a singlet state. This state represents the energies...

UV–Vis Spectroscopy: Molecular Electronic Transitions

UV–Vis Spectroscopy: Molecular Electronic Transitions

In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this...

Photoluminescence: Fluorescence and Phosphorescence

Photoluminescence: Fluorescence and Phosphorescence

Photoluminescence is a process where a molecule absorbs light energy and re-emits it in the form of light. This phenomenon occurs when a substance absorbs photons, promoting its electrons to higher energy level excited states, followed by a relaxation process in which the electrons return to their original ground state energy levels and emit light. Photoluminescence is widely observed in various materials, including semiconductors, and organic and inorganic compounds.
A pair of electrons in a...

¹³C NMR: ¹H–¹³C Decoupling

¹³C NMR: ¹H–¹³C Decoupling

The probability of having two carbon-13 atoms next to each other is negligible because of the low natural abundance of carbon-13. Consequently, peak splitting due to carbon-carbon spin-spin coupling is not observed in spectra. However, protons up to three sigma bonds away split the carbon signal according to the n+1 rule, resulting in complicated spectra.
A broadband decoupling technique is used to simplify these complex, sometimes overlapping, signals. Broadband decoupling relies on a...

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Related Experiment Video

Updated: May 31, 2025

Author Spotlight: Unveiling the Potential of VSFG Microscopy in Studying Mesoscopically Heterogeneous Self-Assembled Structures

Author Spotlight: Unveiling the Potential of VSFG Microscopy in Studying Mesoscopically Heterogeneous Self-Assembled Structures

Published on: December 1, 2023

Photon antibunching in single-molecule vibrational sum-frequency generation.

Fatemeh Moradi Kalarde^1,2, Francesco Ciccarello^1,3, Carlos Sánchez Muñoz^4,5

¹Institute of Physics, Swiss Federal Institute of Technology Lausanne (EPFL), CH-1015 Lausanne, Switzerland.

Nanophotonics (Berlin, Germany)

|January 22, 2025

Summary

This study explores using plasmonic nanocavities for single-molecule vibrational spectroscopy. Researchers found that molecular anharmonicity can create a tunable source of single photons via vibrational blockade.

Keywords:

cavity optomechanics nanocavities photon blockade photonics single photon source vibrational spectroscopy

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Published on: June 8, 2018

Area of Science:

Quantum optics
Molecular spectroscopy
Nanophotonics

Background:

Sum-frequency generation (SFG) is crucial for coherent signal upconversion and mid-infrared vibrational spectroscopy.
Plasmonic nanocavities enhance light confinement, enabling single-molecule detection via surface-enhanced Raman scattering and mid-infrared excitation.

Purpose of the Study:

To compute the second-order coherence (g(2)(0)) of upconverted mid-infrared fields.
To identify operating regimes for preserving mid-infrared source coherence for quantum applications.
To investigate the impact of anharmonic molecular potentials on photon statistics.

Main Methods:

Theoretical computation of the degree of second-order coherence (g(2)(0)).
Modeling of individual molecules with anharmonic potentials.
Analysis under realistic parameters for mid-infrared and visible drives.

Main Results:

Delineation of operating regimes to maintain source coherence.
Demonstration that anharmonic molecular potentials can induce photon antibunching.
Observation of "vibrational blockade" in driven molecules.

Conclusions:

A path towards bright, tunable single-photon sources is established.
Single-photon generation is achieved without strong light-matter coupling.
Leveraging vibrational blockade offers a novel approach for quantum applications.