Maximum entropy (MaxEnt) modelling provides a principled framework for generating synthetic populations from aggregate census data, without access to individual-level microdata. The bottleneck of exact-enumeration approaches is expectation computation by explicit summation over the full tuple space
\cX, which becomes infeasible for more than
K≈20 categorical attributes; sampling-based alternatives exist but rely on Metropolis-type schemes that require proposal tuning and rejection steps. We propose
GibbsPCDSolver, a stochastic replacement for this computation based on Persistent Contrastive Divergence (PCD): a persistent pool of
N synthetic individuals is updated by Gibbs sweeps at each gradient step, providing a stochastic approximation of the model expectations without ever materialising
\cX. We validate the approach on controlled benchmarks and on
Syn-ISTAT, a
K=15 Italian demographic benchmark with analytically exact marginal targets derived from ISTAT-inspired conditional probability tables. Scaling experiments across
K∈{12,20,30,40,50} confirm that GibbsPCDSolver maintains
\MRE∈[0.010,0.018] while
∣\cX∣ grows eighteen orders of magnitude, with runtime scaling as
O(K) rather than
O(∣\cX∣). On Syn-ISTAT, GibbsPCDSolver reaches
\MRE=0.03 on training constraints and -- crucially -- produces populations with effective sample size
\Neff=N versus
\Neff≈0.012N for generalised raking, an
86.8× diversity advantage that is essential for agent-based urban simulations.