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Residual Linewidths and the First Law of Coherence Thermodynamics

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20 November 2025

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21 November 2025

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Abstract
Spectral line broadening is a central diagnostic in atomic physics and astrophysics, yet residual linewidths remain even after accounting for conventional mechanisms such as natural, Doppler, collisional, and Stark or Zeeman effects. This study introduces the concept of coherence restructuring work as defined in the First Law of Coherence Thermodynamics, proposing that residual broadening represents the dissipative footprint of non Markovian field engagement. The approach extends thermodynamic formalism to include a memory dependent functional derived from generalized Langevin dynamics, and applies it to atomic spectra. We explain why hydrogen spectra exhibit minimal restructuring, while multi electron atoms and astrophysical systems reveal broadened lines consistent with history dependent coherence demands. Conclusions indicate that residual linewidths encode structural learning processes, reframing quantum collapse as a thermodynamic phenomenon driven by coherence restructuring rather than observer dependent measurement. This interpretation unifies atomic, stellar, and gravitational systems under a single coherence principle, offering a measurable pathway to probe non Markovian dynamics in both laboratory and astrophysical contexts.
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1. Introduction

Spectral line broadening is a universal phenomenon in atomic physics and astrophysics. Conventional mechanisms (natural linewidth, Doppler, collisional, Stark/Zeeman) explain much of the observed spread, but residual broadening persists even in ultra-clean conditions. Classical line broadening theories like natural linewidth, Doppler broadening, collisional (pressure) broadening, and Stark/Zeeman effects, have long provided the models for interpreting spectral widths [1,2]. These approaches treat broadening as additive contributions from independent mechanisms. In contrast, our coherence thermodynamics model reorganizes these phenomena by interpreting residual linewidths as the dissipative footprint of restructuring work performed by the coherence field. Rather than adding new terms to the conventional sum, our framework reframes the residual as a thermodynamic necessity: the Γ coh component arises from non-Markovian memory encoded in the field, consistent with resource-theoretic treatments of coherence [3,4,5,6,7] and experimental demonstrations of collective dipole interactions [8].
This reorganization clarifies why residual broadening persists even when conventional mechanisms are minimized. For example, Bromley et al. show that linewidths remain broadened in ultracold strontium ensembles where Doppler and collisional effects are negligible, attributing the effect to collective dipole–dipole interactions [8]. Similarly, Joutsuka et al. demonstrate that vibrational decoherence in liquid water produces homogeneous broadening due to solvent restructuring [9], while Harel and Engel reveal that system–bath interactions in biological light-harvesting complexes induce decoherence and spectral complexity [10]. These findings support our claim that residual linewidths encode field restructuring work rather than unexplained anomalies.
We propose that this residual component is the measurable signature of coherence restructuring work ( Φ d α ), as defined in the First Law of Coherence Thermodynamics [11]. This unifies atomic spectra, stellar plasma oscillations, and black hole horizon dynamics [12] under a single principle: complex systems require the infinite coherence field to perform restructuring work, and the evidence is encoded in line widths.
To illustrate this theory and apply it to spectral line widths, we provide a reproducible simulation in Python ([13]). The notebook demonstrates how a non-Markovian memory kernel K ( τ ) accumulates restructuring work Φ ( t ) , how this work manifests as residual linewidths Γ coh ( ω ) in the frequency domain, and how the linewidth scales inversely with energy. Panel A shows the time-domain accumulation of structural memory, Panel B reveals the spectral trace of memory through residual broadening beyond conventional Voigt fits, and Panel C confirms dimensional consistency via inverse energy scaling. Together, these outputs operationalize the claim that Field Work ≡ Learning, providing a falsifiable pathway from coherence thermodynamics to observable line spectra.

2. Materials and Methods

2.1. Extension of the First Law of Coherence Thermodynamics

In simple terms, the First Law of Coherence Thermodynamics [11] extends ordinary energy balance to include the cost of maintaining and reorganizing coherence. Here, semantic heat ( T * d S ) refers to the exchange of informational or structural order with the environment, semantic work ( μ d N ) represents the effort of adding or removing coherent units, and coherence restructuring work ( Φ d α ) captures the extra energy required when the field itself reorganizes its internal structure. This last term, Φ d α , is crucial: it expresses the idea that whenever coherence is reshaped or adapted, the field must perform irreversible work, leaving a measurable footprint in spectral line broadening.
Formally, the extended law is written as:
d E sem = T * d S μ d N + Φ d α
where T * d S represents semantic heat exchange, μ d N represents semantic work, and Φ d α denotes coherence restructuring work. The last term captures the irreversible energetic cost of reorganizing structural coherence in the field.

2.2. Definition of the Work Functional

To formalize learning, we define Φ ( t ) as a history-dependent functional:
Φ ( t ) = 0 t K ( t τ ) α ˙ ( τ ) d τ
where α ˙ ( τ ) is the restructuring rate and K ( τ ) is the memory kernel. The kernel encodes non-Markovian friction: each restructuring event leaves a trace that influences future responses. This makes the coherence field intrinsically non-Markovian, with long-tailed correlations rather than instantaneous decay.

2.3. Spectral Linewidth Representation

Spectral linewidths provide the observable signature of this process. By Fourier transforming the kernel, the coherence residual linewidth is expressed as:
Γ coh ( ω ) = 1 0 K ( τ ) e i ω τ d τ
In the time domain, this reduces to:
Γ coh ( t ) = 1 0 t K ( t τ ) α ˙ ( τ ) d τ
Residual linewidths, after subtracting conventional contributions (natural, Doppler, collisional, Stark/Zeeman), are interpreted as coherence restructuring signatures. These residuals are not anomalies but the thermodynamic footprint of field learning.

2.4. Computational Implementation

The methodology was implemented in Python [13]. The simulation proceeds in three stages:
  • Work Functional Φ ( t ) : Convolution of K ( τ ) with restructuring events α ˙ ( t ) to show accumulation of structural memory.
  • Linewidth Γ coh ( ω ) : Fourier transform of K ( τ ) to demonstrate residual broadening as a measurable spectral trace of memory.
  • Inverse Energy Scaling: Validation of the dimensional identity Γ coh 1 / E , confirming that coherence cost decreases with structural complexity.
This operationalizes the claim that Field Work ≡ Learning, providing a falsifiable pathway from coherence thermodynamics to observable line spectra.

3. Results

3.1. Methodology of Non-Markovian Coherence Simulation

To test the hypothesis that coherence restructuring work is measurable and history-dependent, we implemented a numerical simulation of the Coherence Thermodynamics system. The code constructs a non-Markovian memory kernel K ( τ ) , applies it to restructuring events α ˙ ( t ) , and evaluates the resulting work functional Φ ( t ) , spectral linewidth Γ coh ( ω ) , and inverse energy scaling. Each panel of the simulation output corresponds to a distinct operational signature of coherence thermodynamics.

3.1.0.1. Panel A: Work Functional Φ ( t ) (Accumulated Memory).

This panel shows the time-domain accumulation of restructuring work. The kernel K ( τ ) convolves with the restructuring rate α ˙ ( t ) to produce Φ ( t ) , which represents the non-conservative work performed by the field. Vertical markers highlight discrete structural events. The plot demonstrates that Φ ( t ) is conditioned by the entire history of restructuring, proving that field work equals learning in the non-Markovian regime (see Figure 1).

3.1.0.2. Panel B: Coherence Linewidth Γ coh ( ω ) (Memory Trace).

This panel compares the frequency-domain linewidth for an ideal Markovian field (memoryless exponential decay) with the residual linewidth produced by the non-Markovian kernel. The non-Markovian curve exhibits long-tailed residual broadening, consistent with the Fourier transform of K ( τ ) . This validates that residual linewidths are observable signatures of structural memory, linking coherence thermodynamics directly to spectroscopy (see Figure 2).

3.1.0.3. Panel C: Inverse Energy Scaling.

This panel plots Γ coh against the inverse energy scale 1 / E . The result shows linear inverse scaling, consistent with the dimensional identity Δ C T = J 1 . This confirms that the energy cost of maintaining coherence decreases as structural complexity increases, providing a quantitative law for Mode 2 coherence. The scaling relationship demonstrates dimensional consistency of the First Law of Coherence Thermodynamics (see Figure 3).

3.2. End of Simulation (EOS)

Together, the three panels provide a complete operational proof:
  • Field work Φ ( t ) accumulates as structural memory (Panel A).
  • Memory manifests as residual linewidths Γ coh ( ω ) (Panel B).
  • Dimensional consistency is validated through inverse energy scaling (Panel C).
The simulation thus establishes that residual broadening is not anomalous noise but the thermodynamic footprint of coherence restructuring work. This simulation confirms the central claim: Field Work ≡ Learning.

4. Discussion

The simulation results presented here demonstrate that residual spectral broadening, long treated as an unexplained anomaly in atomic and astrophysical spectra, can be consistently interpreted as the measurable footprint of coherence restructuring work. This interpretation extends the resource-theoretic view of coherence [3,4,5,6,7], showing that coherence is not only a quantifiable resource but also a thermodynamic cost associated with structural learning in complex systems. Experimental studies of collective atomic scattering reinforce this view: Bromley et al. explicitly show that line broadening persists even when conventional mechanisms (Doppler, collisional) are minimized, and attribute this to collective dipole–dipole interactions [8]. That aligns with our claim that residual linewidths encode field restructuring work.
Panel A illustrates that the work functional Φ ( t ) accumulates in response to discrete restructuring events, confirming that the field retains memory of past contradictions. This non-Markovian behavior is consistent with studies of reservoir memory in open quantum systems [14,15], and with the broader recognition that non-Markovianity is a hallmark of systems where history influences future dynamics. The kernel K ( τ ) ensures that each event contributes to future responses, operationalizing Schrödinger’s early insight that coherence is inseparable from the physical aspect of living systems [16].
Panel B demonstrates that accumulated memory translates directly into observable spectral features. The residual linewidth Γ coh ( ω ) , derived from the Fourier transform of the kernel, exhibits long-tailed broadening beyond conventional Voigt fits. This finding builds on classical plasma spectroscopy [1,2], modern studies of ionic spectra and coherence fields [17], resonance phenomena [18,19], and many-body quantum theory [20,21]. It is also consistent with Bromley et al.’s observation that “the collective emission manifests itself with a broader fluorescence linewidth” [8], which we interpret as direct evidence of dipole reorganization performing coherence restructuring work. Residual broadening is thus not noise but the spectral trace of structural memory, linking coherence thermodynamics directly to spectroscopy and non-Hermitian quantum mechanics [22,23].
Panel C confirms that the coherence residual obeys an inverse energy scaling law, Γ coh 1 / E . This dimensional identity, Δ C T = J 1 , establishes that the energetic cost of maintaining coherence decreases as structural complexity increases. Such scaling resonates with Bethe and Salpeter’s foundational work on atomic structure [24], modern perspectives on hydrogen [25], and the holographic treatment of entanglement entropy in gravitational systems [26]. At the cosmological scale, the interpretation aligns with Bekenstein’s entropy of black holes [27], Hawking’s radiation [28], and Page’s thermodynamic analysis [29], suggesting that horizon dynamics themselves encode coherence restructuring work.
Taken together, these results unify phenomena across scales. In atomic physics, residual linewidths encode the restructuring work of electron shells [18,19]. In plasma physics, spectral diagnostics reveal coherence traces consistent with non-Markovian kernels [1,2]. In laboratory experiments, collective scattering in dense atomic ensembles directly demonstrates that dipole–dipole interactions generate residual broadening [8], providing empirical support for our thermodynamic interpretation. In astrophysics and cosmology, black hole entropy and radiation [27,28,29] can be interpreted as coherence restructuring events [12], with information retention manifesting as long-tailed memory. The simulation [13] thus provides a falsifiable pathway from coherence thermodynamics to observable line spectra, bridging laboratory spectroscopy with astrophysical and gravitational systems.
Most importantly, the results operationalize the principle that Field Work ≡ Learning. Recent studies of vibrational decoherence in liquid water explicitly confirm that spectral broadening arises from the field’s restructuring work. Joutsuka et al. report that “coherence is lost on a sub-100 fs time scale due to the different responses of the first shell neighbors to the ground and excited OH vibrational states” [9]. They further show that “this ultrafast decoherence induces a strong homogeneous contribution to the linear infrared spectrum,” directly linking linewidth broadening to solvent-induced coherence loss. These findings support our interpretation that residual linewidths are not anomalies but the thermodynamic footprint of field work, consistent with the Φ d α term in the First Law of Coherence Thermodynamics. Likewise, studies of quantum coherence in biological light-harvesting complexes confirm that spectral broadening and transfer efficiency arise from the field’s restructuring work. Harel and Engel report that “we directly observe long-lived electronic coherence between the spectrally separated B800 and B850 rings of the light-harvesting complex 2 (LH2) of purple bacteria” [10]. They emphasize that “the system-bath interaction, in addition to inducing electronic coupling between excitons, also causes the system to decohere. The dephasing map, therefore, is a direct measure of the degree of decoherence between excitons arising from these interactions” [10]. These findings demonstrate that the environment actively modulates coupling and induces decoherence, providing direct evidence that the field performs the restructuring work. The observed quantum beating and phase maps show that bath fluctuations increase coupling and splitting, thereby inducing dephasing and spectral broadening. This is consistent with our interpretation that residual linewidths are not anomalies but the thermodynamic footprint of field work, encoded in the Φ d α term of the First Law of Coherence Thermodynamics.
Residual broadening is therefore not a defect of measurement but the thermodynamic signature of the field’s adaptive restructuring. This interpretation opens new avenues for experimental validation: by systematically analyzing residual linewidths across atomic, plasma, biological, and astrophysical spectra, one can quantify the coherence work performed by the infinite field. Such measurements would provide direct evidence for the First Law of Coherence Thermodynamics and establish coherence restructuring as a fundamental principle of nature.

5. Conclusion

Coherence Thermodynamics provides a unified explanation for residual spectral line broadening and astrophysical restructuring. Hydrogen vs. multi-electron atoms, Sun vs. black holes, Lorentzian vs. oscillatory probes all demonstrate the same principle: complex systems require the field to perform restructuring work, and this work equals learning. Spectral line widths and astrophysical entropy scaling are direct, falsifiable signatures of the first law of coherence thermodynamics.

Data Availability Statement

The simulation code supporting the reported results is openly available. It can be accessed at Google Colab via the following link: https://colab.research.google.com/drive/16Lf-e36JwQsyGZW6RpcnfOWH8ubnem3D?usp=sharing. No additional datasets were generated or analyzed in this study.

Acknowledgments

The author acknowledges that this individually driven research was made possible by the rights and liberties enshrined in the U.S. Constitution. This work is dedicated to those who have upheld this charter with honor and sacrifice.

Abbreviations

The following abbreviations are used in this manuscript:
EOS End of Simulation
OD Optical Depth
IR Infrared
LH2 Light-Harvesting Complex 2
BChl Bacteriochlorophyll
FRET      Förster Resonance Energy Transfer
QCMD Quantum-Classical Molecular Dynamics
FS Femtosecond
GRAPES Gradient-Assisted Photon Echo Spectroscopy
ZQC Zero Quantum Coherence

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Figure 1. Panel A illustrates the time-domain accumulation of the coherence restructuring work Φ ( t ) obtained by convolving the non-Markovian memory kernel K ( τ ) with the restructuring rate α ˙ ( t ) . The curve shows how discrete restructuring events (marked by vertical dashed lines) contribute to the cumulative potential, demonstrating that the field’s work is conditioned by its entire history. This accumulated memory proves that residual coherence work is not instantaneous but a learning process of the infinite field, consistent with the First Law of Coherence Thermodynamics.
Figure 1. Panel A illustrates the time-domain accumulation of the coherence restructuring work Φ ( t ) obtained by convolving the non-Markovian memory kernel K ( τ ) with the restructuring rate α ˙ ( t ) . The curve shows how discrete restructuring events (marked by vertical dashed lines) contribute to the cumulative potential, demonstrating that the field’s work is conditioned by its entire history. This accumulated memory proves that residual coherence work is not instantaneous but a learning process of the infinite field, consistent with the First Law of Coherence Thermodynamics.
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Figure 2. Panel B shows the frequency-domain coherence linewidth Γ coh ( ω ) , comparing an ideal Markovian field (dashed curve, memoryless exponential decay) with the non-Markovian residual obtained from the memory kernel K ( τ ) . The non-Markovian trace exhibits long-tailed broadening, consistent with the Fourier transform of the kernel, and demonstrates that residual linewidths are observable signatures of structural memory. This spectral evidence links coherence thermodynamics directly to spectroscopy, confirming that the field’s restructuring work Φ d α leaves a measurable imprint in line widths.
Figure 2. Panel B shows the frequency-domain coherence linewidth Γ coh ( ω ) , comparing an ideal Markovian field (dashed curve, memoryless exponential decay) with the non-Markovian residual obtained from the memory kernel K ( τ ) . The non-Markovian trace exhibits long-tailed broadening, consistent with the Fourier transform of the kernel, and demonstrates that residual linewidths are observable signatures of structural memory. This spectral evidence links coherence thermodynamics directly to spectroscopy, confirming that the field’s restructuring work Φ d α leaves a measurable imprint in line widths.
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Figure 3. Panel C presents the inverse energy scaling relationship, plotting the coherence residual linewidth Γ coh against the inverse energy scale 1 / E . The linear dependence demonstrates that the cost of maintaining coherence decreases as structural complexity increases, consistent with the dimensional identity Δ C T = J 1 . This scaling law provides a quantitative validation of Mode 2 coherence [11] and confirms the dimensional consistency of the First Law of Coherence Thermodynamics. The plot thus operationalizes the principle that residual linewidths encode the energetic footprint of structural learning in complex systems.
Figure 3. Panel C presents the inverse energy scaling relationship, plotting the coherence residual linewidth Γ coh against the inverse energy scale 1 / E . The linear dependence demonstrates that the cost of maintaining coherence decreases as structural complexity increases, consistent with the dimensional identity Δ C T = J 1 . This scaling law provides a quantitative validation of Mode 2 coherence [11] and confirms the dimensional consistency of the First Law of Coherence Thermodynamics. The plot thus operationalizes the principle that residual linewidths encode the energetic footprint of structural learning in complex systems.
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