Organic molecule fluorescence as an experimental test-bed for quantum jumps in thermodynamics

The development of spectroscopic techniques able to detect and verify quantum coherence is a goal of increasing importance given the rapid progress of new quantum technologies, the advances in the field of quantum thermodynamics, and the emergence of new questions in chemistry and biology regarding the possible relevance of quantum coherence in biochemical processes. Ideally, these tools should be able to detect and verify the presence of quantum coherence in both the transie...

Cooling atoms to ultralow temperatures has produced a wealth of opportunities in fundamental physics, precision metrology, and quantum science. The more recent application of sophisticated cooling techniques to molecules, which has been more challenging to implement due to the complexity of molecular structures, has now opened door to the longstanding goal of precisely controlling molecular internal and external degrees of freedom and the resulting interaction processes. This...

Ensemble averaging of molecular states is fundamental for the experimental determination of thermodynamic quantities. A special case occurs for single-molecule investigations under equilibrium conditions, for which free energy, entropy and enthalpy at finite-temperatures are challenging to determine with ensemble-averaging alone. Here, we provide a method to access single-molecule thermodynamics, by confining an individual molecule to a nanoscopic pore of a two-dimensional me...

The key factors determining the emission bandwidth of thermally activated delayed fluorescence (TADF) are investi-gated by combining computational and experimental approaches. To achieve high internal quantum efficiencies (IQEs) in metal-free organic light emitting diode via TADF, the first triplet (T1) to first singlet (S1) reverse intersystem crossing (rISC) is promoted by configuring molecules in an electron donor-acceptor (D-A) alternation with a large di-hedral angle, wh...

We studied the spectral dynamics of single fluorescent dye molecules embedded in ultrathin films (5 - 100 nm) of the amorphous polymer polyisobutylene at cryogenic temperatures and its variation with film thickness. Noticeable portion of molecules in the ensemble show a behavior which is inconsistent with the standard tunneling model: Their spectral lines are subject to irreversible spectral jumps, continuous shifting, and abrupt chaotic changes of the linewidth or jumping ra...

We describe a method to probe the spectral fluctuations of a transition over broad ranges of frequencies and timescales with the high spectral resolution of Fourier spectroscopy, and a temporal resolution as high as the excited state lifetime, even in the limit of very low photocounting rates. The method derives from a simple relation between the fluorescence spectral dynamics of a single radiating dipole and its fluorescence intensity correlations at the outputs of a continu...

The extraordinary success in laser cooling, trapping, and coherent manipulation of atoms has energized the efforts in extending this exquisite control to molecules. Not only are molecules ubiquitous in nature, but the control of their quantum states offers unparalleled access to fundamental constants and possible physics beyond the Standard Model. Quantum state manipulation of molecules can enable high-precision measurements including tests of fundamental symmetries and searc...

Single molecules are nanoscale thermodynamic systems with few degrees of freedom. Thus, the knowledge of their entropy can reveal the presence of microscopic electron transfer dynamics, that are difficult to observe otherwise. Here, we apply thermocurrent spectroscopy to directly measure the entropy of a single free radical molecule in a magnetic field. Our results allow us to uncover the presence of a singlet to triplet transition in one of the redox states of the molecule, ...

Understanding heat transport is relevant to develop efficient strategies for thermal management in microelectronics for instance, as well as for fundamental science purposes. However, measuring temperatures in nanostructured environments and in cryogenic conditions remains a challenging task, that requires both high sentitivity and a non-invasive approach. Here we present a portable nanothermometer based on a molecular two-level quantum system that operates in the 3 - 30 K te...

The advent of single molecule optics has had a profound impact in fields ranging from biophysics to material science, photophysics, and quantum optics. However, all existing room-temperature single molecule methods have been based on fluorescence detection of highly efficient emitters. Here we demonstrate that standard, modulation-free measurements known from conventional absorption spectrometers can indeed detect single molecules. We report on quantitative measurements of th...