Thermodynamic Dissipation Theory for Life

• The theory posits that life emerged to maximize entropy production, applying non-equilibrium thermodynamic principles to UVC-induced molecular transformations.
• It demonstrates that autocatalytic nucleic acid replication and UVC absorption structured early molecular evolution through a dissipation–replication feedback mechanism.
• Empirical correlations between amino acid traits and codon affinities suggest that genetic information evolved as a record of optimal energy dissipation strategies.

Thermodynamic Dissipation Theory for the Origin of Life is a comprehensive framework attributing life's emergence and early molecular evolution to the imperative of maximizing entropy production under non-equilibrium boundary conditions, typically driven by intense solar photon fluxes and environmental gradients. Central to this theory is the assertion that self-organization, replication, and information encoding in primordial molecules can be quantitatively understood as autocatalytic processes that more effectively dissipate externally imposed energy potentials—particularly UVC photons during the Archean—via classical irreversible thermodynamics and non-linear entropy-production principles.

1. Non-Equilibrium Thermodynamic Principles and Dissipative Structures

Life is fundamentally described as a hierarchy of dissipative structures—self-organizing systems that accelerate entropy production by promoting irreversible energy flows toward equilibrium (Mejía et al., 2018). The governing equation for local entropy production is: $\sigma = \sum_i J_i X_i$ where $J_i$ represents generalized irreversible fluxes (e.g., heat, matter), and $X_i$ denotes conjugate thermodynamic forces (e.g., temperature or chemical potential gradients). Prigogine’s and Onsager’s work formalizes the Maximum Entropy Production Principle (MEPP): when an external potential is imposed (such as solar photons at Earth's surface), new structures or processes will emerge if such emergence increases collective entropy production. The autocatalytic formation and proliferation of molecular assemblies that dissipate imposed free-energy potentials (such as UV-absorbing nucleic acids) are thus thermodynamically favored (Michaelian, 2013, 0907.0042).

2. Archean Environmental Context: UVC Flux and Photochemical Structuring

During the Archean (ca. 3.8–2.7 Ga), Earth’s surface was exposed to a considerable flux of long-wavelength UVC (200–290 nm), measured at up to ~5 W·m⁻² at midday near the equator (Mejía et al., 2018). Simple molecules like HCN, prevalent in oceanic microlayers, absorbed UVC photons and, through photochemical transformations, converted into purines and pyrimidines—nucleobase chromophores possessing high molar extinction coefficients (ε ~ 5×10³–10⁴ M⁻¹·cm⁻¹) precisely matching the Archean UVC window (Michaelian, 2020, Michaelian et al., 2014). These nucleobases exhibited ultrafast non-radiative decay channels (conical intersections) that transformed excitation into vibrational heat on sub-picosecond timescales, ensuring maximal local entropy production. The empirical ubiquity of efficient UVC dissipative biomolecules across Bacteria, Archaea, and Eukarya constitutes evidence for their spontaneous emergence via dissipative structuring under solar photon potentials (Michaelian et al., 2014, Michaelian, 2013).

3. Dissipation–Replication Feedback and UVTAR Mechanism

Dissipative structuring develops autocatalytic features when the reaction products themselves catalyze dissipation of the same imposed potential that produced them ("dissipation–replication" relation). Archean nucleic acids—both single and double-stranded DNA/RNA—acted as agents of both photochemical synthesis and UVC absorption, photocatalyzing further production of RNA/DNA molecules (Mejía et al., 2018). Formally, the steady-state pigment concentration satisfies: $$\frac{dC}{dt} = k_1 P - k_2 C \implies C^* = \frac{k_1}{k_2} P$$ with $k_1 \propto C$ for autocatalysis. The UVC–Temperature-Assisted Replication (UVTAR) mechanism operated as follows:

• Day: UVC absorption by ds nucleic acids raised local T above melting point ($T_m$), denaturing into single strands (hyperchromism: ssDNA/RNA absorbs 30–40% more UVC).
• Night: Cooling ($\Delta T \sim 3–5^\circ$C) facilitated Mg²⁺-mediated template-directed extension, reforming ds structures.

This cycle integrates dissipation (UVC→heat) directly with replication, yielding exponential autocatalytic proliferation of sequences optimized for UVC dissipation (0907.0042, Sawada et al., 2020).

4. Correlations Between Physicochemical Properties and Sequence Information

Empirical investigations reveal strong correlations between dissipation-enhancing amino acid traits and their codon/anticodon affinities (Mejía et al., 2018). Amino acids most effectively maintaining nucleic acids at the surface (amphipathic, aromatic, charged, catalytic) also display the highest stereochemical affinity for their respective codons/anticodons (Yarus et al.), facilitating enhanced photon dissipation and replication rates. Table 1 from Michaelian & Mejía (2018) quantifies this correlation (Corr P < 10⁻⁴), supporting the view that information encoding in nucleic acids originated as a record of successful dissipative strategies.

Dissipation Trait	Relevant Amino Acids	Codon/Anticodon Affinity (Empirical)
Amphipathic (surface retention)	Trp, Met, Tyr, Lys	High
Aromatic/charge-transfer (Förster antenna)	Trp, Phe, Tyr	High
Planar intercalator (helix stabilization)	Trp, Phe	High
Positively charged (phosphate neutralization)	Lys, Arg, His	High
Catalytic (acid-base/redox)	His, Asp, Glu	High

This stereochemical mapping supports the hypothesis that genetic information accumulation is fundamentally thermodynamic: base triplets encode recruitment of amino acids yielding maximal entropy production (Mejía et al., 2018).

5. Generalizations: Dissipation-Driven Selection in Chemical Networks and Fluids

Extensions of the dissipation theory to chemical networks and fluids highlight the universality of dissipation-driven selection. In non-equilibrium chemical systems subject to temperature gradients—and modeled via master equations with Arrhenius rates—states participating in faster reactions and dissipating more heat become exponentially stabilized (Busiello et al., 2019). The selection ratio: $$R_{CB} = \frac{P(C)}{P(B)} = 1 + \frac{\Delta E}{4 T^4} \Delta \epsilon (\Delta T)^2 + \mathcal{O}((\Delta T)^3)$$ demonstrates preferential population of states at the termini of fastest-dissipating pathways. In incompressible liquids governed by Lennard-Jones potentials, the appearance of self-ordered structures (vortices, patterns) is linked to increases in generalized free energy ($\Delta \Psi_{system} > 0$), occurring at the expense of local entropy ($\Delta S_{system} < 0$), reconciling the emergence of order from dissipative processes (Chiarelli, 2013).

6. Thermodynamic Foundation for Information Encoding and Darwinian Selection

Persistence of molecular sequence structures directly equates to information storage about past successful dissipation strategies under non-equilibrium conditions. Base triplets encoding amino acids that optimize both photon dissipation and UVTAR replication embody molecular blueprints maximizing entropy production ($\sigma_{total}$). Sequence evolution thus seeks not only chemical functionality but also superior dissipative efficacy—a thermodynamic analogue to Darwinian natural selection (Mejía et al., 2018, Sawada et al., 2020).

The key thermodynamic selection criterion is: $$\text{Maximize} \; \frac{\partial \sigma_{total}}{\partial C}$$ for any candidate molecular assembly, ensuring that those producing more entropy per added molecule proliferate fastest.

7. Broader Theoretical Developments and Experimental Implications

Modern treatments generalize the second law for far-from-equilibrium self-replicating systems (e.g., England–Crooks fluctuation theorem): $$\beta \langle \Delta Q \rangle + \Delta S_{int} \geq \ln \left( \frac{g}{\delta} \right)$$ where $g$ and $\delta$ are replication and decay rates, respectively (Marsh, 2022). Dissipative adaptation frameworks quantify the statistical preference for configuration-trajectories with maximal irreversible work absorption, selecting self-replicators that most efficiently transduce ambient energy into heat.

Various experimental models—wet–dry cycling nucleotide synthesis, photochemical replication, controlled microfluidics, and synthetic ribozyme systems—are being investigated to test correlations between replication/growth rates and entropy production. These studies validate the prediction that molecular assemblies optimized for energy dissipation dominate evolutionary trajectories, providing experimental access to the theory’s core postulates.

Summary

Thermodynamic Dissipation Theory for the Origin of Life posits that the externally imposed Archean photon potential universally drove molecular self-organization, replication, and information encoding. Nucleic acids and their earliest amino acid partners emerged as dissipative structures specifically engineered by natural selection for optimal UVC photon dissipation and autocatalytic replication (UVTAR). The observed correlations between codon/anticodon affinities and amino acid physicochemical properties—fomenting enhanced photon dissipation—constitute molecular imprints of this selection mechanism. This non-equilibrium thermodynamic foundation reconciles the emergence of biological information storage and Darwinian selection with the physical imperative of maximizing entropy production under planetary energy flows (Mejía et al., 2018, 0907.0042, Marsh, 2022, Michaelian et al., 2014, Michaelian, 2013, Chiarelli, 2013, Busiello et al., 2019, Sawada et al., 2020, Michaelian, 2020).